U.S. patent application number 16/533144 was filed with the patent office on 2019-11-28 for curable composition, cured film, light blocking film, solid-state imaging element, solid-state imaging device, and manufacturing.
This patent application is currently assigned to FUJIFILM Corporation. The applicant listed for this patent is FUJIFILM Corporation. Invention is credited to Tatsuo ISHIKAWA, Yoshinori Taguchi.
Application Number | 20190359825 16/533144 |
Document ID | / |
Family ID | 63585942 |
Filed Date | 2019-11-28 |











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United States Patent
Application |
20190359825 |
Kind Code |
A1 |
ISHIKAWA; Tatsuo ; et
al. |
November 28, 2019 |
CURABLE COMPOSITION, CURED FILM, LIGHT BLOCKING FILM, SOLID-STATE
IMAGING ELEMENT, SOLID-STATE IMAGING DEVICE, AND MANUFACTURING
METHOD OF CURED FILM
Abstract
An object of the present invention is to provide a curable
composition which has excellent patterning properties and makes it
possible to obtain a cured film having excellent light blocking
properties. Another object of the present invention is to provide a
cured film, a light blocking film, a solid-state imaging element,
and a solid-state imaging device. The curable composition contains
inorganic particles, a polymerizable compound, and a polymerization
initiator, in which the inorganic particles contain metal
carbide-containing particles containing a carbide of an element in
group 5 of the periodic table, and a content of the metal
carbide-containing particles in a total mass of the inorganic
particles is equal to or greater than 55% by mass.
Inventors: |
ISHIKAWA; Tatsuo;
(Haibara-gun, JP) ; Taguchi; Yoshinori;
(Haibara-gun, JP) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
FUJIFILM Corporation |
Tokyo |
|
JP |
|
|
Assignee: |
FUJIFILM Corporation
Tokyo
JP
|
Family ID: |
63585942 |
Appl. No.: |
16/533144 |
Filed: |
August 6, 2019 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
|
|
PCT/JP2018/007996 |
Mar 2, 2018 |
|
|
|
16533144 |
|
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Current U.S.
Class: |
1/1 |
Current CPC
Class: |
C08L 2203/16 20130101;
C09D 133/08 20130101; C08K 2201/003 20130101; C08L 2203/20
20130101; C09D 133/08 20130101; C08G 73/1042 20130101; C08L 33/12
20130101; C09D 133/08 20130101; C08G 73/106 20130101; C08J 5/18
20130101; C08L 79/08 20130101; C08K 3/14 20130101; C08K 3/14
20130101; C08L 79/08 20130101; C08K 3/14 20130101; C08J 3/28
20130101; C08G 73/1082 20130101 |
International
Class: |
C08L 79/08 20060101
C08L079/08; C08K 3/14 20060101 C08K003/14; C08J 5/18 20060101
C08J005/18; C08L 33/12 20060101 C08L033/12; C08J 3/28 20060101
C08J003/28 |
Foreign Application Data
Date |
Code |
Application Number |
Mar 21, 2017 |
JP |
2017-054724 |
Claims
1. A curable composition comprising: inorganic particles; a
polymerizable compound; and a polymerization initiator, wherein the
inorganic particles contain metal carbide-containing particles
containing a carbide of an element in group 5 of the periodic
table, and a content of the metal carbide-containing particles in a
total mass of the inorganic particles is equal to or greater than
55% by mass.
2. The curable composition according to claim 1, wherein a ratio of
a mass of the polymerizable compound contained in the curable
composition to a mass of the inorganic particles contained in the
curable composition is 0.1 to 0.8.
3. The curable composition according to claim 1, further
comprising: a polymerization inhibitor.
4. The curable composition according to claim 2, further
comprising: a polymerization inhibitor.
5. The curable composition according to claim 3, wherein a ratio of
a mass of the polymerization inhibitor contained in the curable
composition to a mass of the inorganic particles contained in the
curable composition is 0.0001 to 0.0005.
6. The curable composition according to claim 4, wherein a ratio of
a mass of the polymerization inhibitor contained in the curable
composition to a mass of the inorganic particles contained in the
curable composition is 0.0001 to 0.0005.
7. The curable composition according to claim 1, further
comprising: a resin.
8. The curable composition according to claim 7, wherein the resin
contains an alkali-soluble resin, and a ratio of a mass of the
alkali-soluble resin contained in the curable composition to a mass
of the inorganic particles contained in the curable composition is
0.03 to 0.6.
9. The curable composition according to claim 1, wherein an average
primary particle diameter of the metal carbide-containing particles
is greater than 5 nm and less than 200 nm.
10. The curable composition according to claim 1, wherein the
element is Ta.
11. The curable composition according to claim 1, wherein the
element is Nb or V.
12. A cured film obtained by curing the curable composition claim
1.
13. A light blocking film comprising: the cured film according to
claim 12.
14. A solid-state imaging element comprising: the cured film
according to claim 12.
15. An image display device comprising: the cured film according to
claim 12.
16. A manufacturing method of a cured film, comprising: a curable
composition layer forming step of forming a curable composition
layer by using the curable composition according to claim 1; an
exposure step of exposing the curable composition layer by
irradiating the curable composition layer with actinic rays or
radiation; and a development step of developing the exposed curable
composition layer so as to form a cured film.
Description
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] This application is a Continuation of PCT International
Application No. PCT/JP2018/007996 filed on Mar. 2, 2018, which
claims priority under 35 U.S.C .sctn. 119(a) to Japanese Patent
Application No. 2017-054724 filed on Mar. 21, 2017. Each of the
above application(s) is hereby expressly incorporated by reference,
in its entirety, into the present application.
BACKGROUND OF THE INVENTION
1. Field of the Invention
[0002] The present invention relates to a curable composition, a
cured film, a light blocking film, a solid-state imaging element, a
solid-state imaging device, and a manufacturing method of a cured
film.
2. Description of the Related Art
[0003] In the related art, as particles incorporated into a curable
composition for manufacturing a cured film having light blocking
properties (hereinafter, referred to as "light blocking film" as
well), metal nitride-containing particles are known. The metal
nitride-containing particles are used for various purposes.
Particularly, the curable composition containing the metal
nitride-containing particles has been used, for example, for
preparing a light blocking film that a solid-state imaging element
(for example, a liquid crystal display device, an organic
electroluminescence (EL) device, or the like), a solid-state
imaging device, and the like comprise.
[0004] Specifically, a color filter that a solid-state imaging
device and the like comprise includes a light blocking film called
black matrix for the purpose of blocking light between colored
pixels, enhancing contrast, and the like.
[0005] A solid-state imaging element comprises a light blocking
film for the purpose of preventing the occurrence of noise,
improving image quality, and the like. Currently, a compact and
thin solid-state imaging device is mounted on mobile terminals such
as a mobile phone and Personal Digital Assistant (PDA). Generally,
the solid-state imaging device comprises a solid-state imaging
element such as a Charge Coupled Device (CCD) image sensor and a
Complementary Metal-Oxide Semiconductor (CMOS) image sensor and a
lens for forming an image of an object on the solid-state imaging
element.
[0006] As the curable composition for manufacturing the cured film
described above, a photosensitive black resin composition, which
contains a light blocking material, an alkali-soluble resin, a
polymerization initiator, a reactive monomer, and an organic
solvent, contains at least titanium nitride particles as the light
blocking material, and can form a coating film having predetermined
optical characteristics, is described in JP2010-097210A.
[0007] Furthermore, JP2010-095716A describes a light blocking
material in which a compositional ratio between titanium nitride
particles and titanium carbide particles is within a range of 80/20
to 20/80 based on mass.
SUMMARY OF THE INVENTION
[0008] The inventors of the present invention examined the
photosensitive black resin composition described in JP2010-097210A.
As a result, the inventors have found that although a cured film
obtained from the composition has excellent light blocking
properties, patterning properties of the photosensitive black resin
composition have problems. Furthermore, the inventors of the
present invention have found that the light blocking material
containing titanium carbide particles described in JP2010-095716A
has problems with light blocking properties. The inventors have
also found that in a case where the content of a pigment such as
titanium nitride-containing particles in the curable composition is
increased so as to obtain a light blocking film having excellent
light blocking properties, the pigment is easily precipitated, and
hence the temporal stability of the curable composition becomes
problematic.
[0009] Therefore, an object of the present invention is to provide
a curable composition which has excellent temporal stability and
excellent patterning properties and makes it possible to obtain a
light blocking film having excellent light blocking properties.
Another object of the present invention is to provide a cured film,
a light blocking film, a solid-state imaging element, a solid-state
imaging device, and a manufacturing method of a cured film.
[0010] In order to achieve the above objects, the inventors of the
present invention conducted an intensive study. As a result, the
inventors have found that the objects can be achieved by the
following constitution.
[0011] [1] A curable composition containing inorganic particles, a
polymerizable compound, and a polymerization initiator, in which
the inorganic particles contain metal carbide-containing particles
containing a carbide of an element in group 5 of the periodic
table, and a content of the metal carbide-containing particles in a
total mass of the inorganic particles is equal to or greater than
55% by mass.
[0012] [2] The curable composition described in [1], in which a
ratio of a mass of the polymerizable compound contained in the
curable composition to a mass of the inorganic particles contained
in the curable composition is 0.1 to 0.8.
[0013] [3] The curable composition described in [1] or [2], further
containing a polymerization inhibitor.
[0014] [4] The curable composition described in [3], in which a
ratio of a mass of the polymerization inhibitor contained in the
curable composition to a mass of the inorganic particles contained
in the curable composition is 0.0001 to 0.0005.
[0015] [5] The curable composition described in any one of [1] to
[4], further containing a resin.
[0016] [6] The curable composition described in [5], in which the
resin contains an alkali-soluble resin, and a ratio of a mass of
the alkali-soluble resin contained in the curable composition to a
mass of the inorganic particles contained in the curable
composition is 0.03 to 0.6.
[0017] [7] The curable composition described in any one of [1] to
[6], in which an average primary particle diameter of the metal
carbide-containing particles is greater than 5 nm and less than 200
nm.
[0018] [8] The curable composition described in any one of [1] to
[7], in which the element is Ta.
[0019] [9] The curable composition described in any one of [1] to
[7], in which the element is Nb or V.
[0020] [10] A cured film obtained by curing the curable composition
described in any one of [1] to [9].
[0021] [11] A light blocking film containing the cured film
described in [10].
[0022] [12] A solid-state imaging element containing the cured film
described in [10].
[0023] [13] An image display device containing the cured film
described in [10].
[0024] [14] A manufacturing method of a cured film, including a
curable composition layer forming step of forming a curable
composition layer by using the curable composition described in any
one of [1] to [9], an exposure step of exposing the curable
composition layer by irradiating the curable composition layer with
actinic rays or radiation, and a development step of developing the
exposed curable composition layer so as to form a cured film.
[0025] According to the present invention, a curable composition
can be provided which has excellent temporal stability and
excellent patterning properties and makes it possible to obtain a
light blocking film having excellent light blocking properties.
Furthermore, the present invention can provide a cured film, a
light blocking film, a solid-state imaging element, and a
solid-state imaging device.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] FIG. 1 is a schematic cross-sectional view showing an
example of the constitution of a solid-state imaging device.
[0027] FIG. 2 is an enlarged schematic cross-sectional view showing
an imaging portion in FIG. 1.
[0028] FIG. 3 is a schematic cross-sectional view showing an
example of the constitution of an infrared sensor.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] Hereinafter, the present invention will be specifically
described.
[0030] The following constituents will be described based on
typical embodiments of the present invention in some cases, but the
present invention is not limited to the embodiments.
[0031] In the present specification, a range of numerical values
described using "to" means a range including the numerical values
listed before and after "to" as a lower limit and an upper limit
respectively.
[0032] In the present specification, regarding the description of a
group (atomic group), in a case where whether the group is
substituted or unsubstituted is not described, the group includes a
group which does not have a substituent and a group which has a
substituent. For example, "alkyl group" includes not only an alkyl
group which does not have a substituent (unsubstituted alkyl group)
but also an alkyl group which has a substituent (substituted alkyl
group).
[0033] Furthermore, in the present specification, "actinic rays" or
"radiation" means, for example, far ultraviolet rays, extreme
ultraviolet radiation (EUV: extreme ultraviolet), X-rays, electron
beams, and the like. In addition, in the present specification,
light means actinic rays and radiation. In the present
specification, unless otherwise specified, "exposure" includes not
only exposure by far ultraviolet rays, X-rays, and EUV, but also
lithography by particle beams such as electron beams and ion
beams.
[0034] In the present specification, "(meth)acrylate" represents
acrylate and methacrylate, "(meth)acryl" represents acryl and
methacryl, "(meth)acryloyl" represents acryloyl and methacryloyl,
and "(meth)acrylamide" represents acrylamide and methacrylamide.
Furthermore, in the present specification, "tanryotai" in Japanese
and "monomer" have the same definition. The monomer is classified
into an oligomer and a polymer, and refers to a compound having a
weight-average molecular weight equal to or smaller than 2,000. In
the present specification, a polymerizable compound refers to a
compound containing a polymerizable group, and may be a monomer or
a polymer. The polymerizable group refers to a group which takes
part in a polymerization reaction.
[0035] [Curable Composition]
[0036] The curable composition according to an embodiment of the
present invention contains inorganic particles, a polymerizable
compound, and a polymerization initiator, in which the inorganic
particles contain metal carbide-containing particles containing a
carbide of an element in group 5 of the periodic table, and a
content of the metal carbide-containing particles in the inorganic
particles is equal to or greater than 55% by mass with respect to a
total mass of the inorganic particles.
[0037] The curable composition according to the embodiment has the
effects of the present invention. Details of the mechanism are
unclear but are assumed to be as below according to the inventors
of the present invention.
[0038] The curable composition according to the embodiment contains
metal carbide-containing particles containing a carbide of an
element in group 5 of the periodic table. The elements in group 5
of the periodic table have a higher specific gravity compared to,
for example, titanium and the like, and among the elements having
the same mass, the elements in group 5 have a small volume.
Therefore, in a case where the metal carbide-containing particles
are added to the curable composition at a certain mass ratio,
because the total volume thereof is smaller than that of titanium
nitride and the like, the metal carbide-containing particles can be
more easily dispersed in the curable composition. Accordingly,
considering the overall makeup of the curable composition, the
content of the polymerizable compound (and the content of other
optional components such as the content of a resin and the like
which will be described later) can be increased. Presumably, for
this reason, the curable composition according to the embodiment
may have better patterning properties.
[0039] Hereinafter, each of the components contained in the curable
composition according to the embodiment of the present invention
will be described.
[0040] [A: Inorganic Particles]
[0041] The curable composition according to the embodiment contains
inorganic particles. The inorganic particles are not particularly
limited as long as they contain metal carbide-containing particles
containing a carbide of an element in group 5 of the periodic table
(hereinafter, simply referred to as "metal carbide-containing
particles" as well), and the content of the metal
carbide-containing particles is equal to or greater than 55% by
mass with respect to the total mass of the inorganic particles.
[0042] The content of the inorganic particles in the curable
composition is not particularly limited. Generally, the content of
the inorganic particles with respect to the total solid content of
the curable composition is 20% to 70% by mass, more preferably 30%
to 65% by mass, and even more preferably 40% to 62% by mass. One
kind of inorganic particles may be used singly, or two or more
kinds of inorganic particles may be used in combination. In a case
where two or more kinds of inorganic particles are used in
combination, the total content thereof is preferably within the
above range.
[0043] A ratio of the mass of the polymerizable compound (B), which
will be described later, contained in the curable composition to
the mass of the inorganic particles (A), which will be described
later, contained in the curable composition (B/A) is not
particularly limited. In order for the curable composition to have
better temporal stability and better patterning properties, B/A is
preferably equal to or higher than 0.01, more preferably equal to
or higher than 0.05, and even more preferably equal to or higher
than 0.1. Furthermore, in order for the curable composition to have
better patterning properties, the upper limit of B/A is preferably
equal to or lower than 1.0, more preferably equal to or lower than
0.95, even more preferably equal to or lower than 0.85, and
particularly preferably equal to or lower than 0.8.
[0044] A ratio of the mass of the polymerization initiator (C),
which will be described later, contained in the curable composition
to the mass of the inorganic particles (A) contained in the curable
composition (C/A) is not particularly limited. Generally, C/A is
preferably 0.01 to 0.2. In a case where C/A is within the above
range, the curable composition has further improved effects of the
present invention.
[0045] A ratio of the mass of the polymerization inhibitor (D),
which will be described later, contained in the curable composition
to the mass of the inorganic particles (A) contained in the curable
composition (D/A) is not particularly limited. In order for the
curable composition to have better temporal stability and
patterning properties, D/A is preferably equal to or higher than
0.00001, and more preferably 0.0001. The upper limit of D/A is not
particularly limited. In order for the curable composition to have
better patterning properties, the upper limit of D/A is preferably
equal to or lower than 0.001, more preferably equal to or lower
than 0.0008, even more preferably equal to or lower than 0.0007,
and particularly preferably equal to or lower than 0.0005.
[0046] A ratio of the mass of a dispersant (E1), which will be
described later, contained in the curable composition to the mass
of the inorganic particles (A) contained in the curable composition
(E1/A) is not particularly limited. In order for the curable
composition to have better temporal stability and better patterning
properties, E1/A is preferably equal to or higher than 0.01, more
preferably equal to or higher than 0.1, and even more preferably
equal to or higher than 0.2. The upper limit of E1/A is not
particularly limited, but is preferably equal to or lower than 1.0
and more preferably equal to or lower than 0.8 in general.
[0047] A ratio of the mass of an alkali-soluble resin (E2), which
will be described later, contained in the curable composition to
the mass of the inorganic particles (A) contained in the curable
composition (E2/A) is not particularly limited. In order for the
curable composition to have better patterning properties, E2/A is
preferably equal to or higher than 0.001, more preferably equal to
or higher than 0.01, even more preferably equal to or higher than
0.015, and particularly preferably equal to or higher than 0.03.
The upper limit of E2/A is not particularly limited. Generally, in
order for the curable composition to have better patterning
properties, the upper limit of E2/A is preferably equal to or lower
than 1.0, more preferably equal to or lower than 0.8, and even more
preferably equal to or lower than 0.6.
[0048] A ratio of the mass of a surfactant (F), which will be
described later, contained in the curable composition to the mass
of the inorganic particles (A) contained in the curable composition
(F/A) is not particularly limited. Generally, F/A is preferably
0.0001 to 0.01, and more preferably 0.001 to 0.003. In a case where
F/A is within the above range, the curable composition has further
improved effects of the present invention.
[0049] <A1: Metal Carbide-Containing Particles>
[0050] The inorganic particles contain metal carbide-containing
particles.
[0051] The content of the metal carbide-containing particles in the
total mass of the inorganic particles is equal to or greater than
55% by mass. In a case where the content of the metal
carbide-containing particles in the inorganic particles is equal to
or greater than 55% by mass, the curable composition has better
light blocking properties and patterning properties.
[0052] The content of the metal carbide-containing particles in the
inorganic particles is preferably equal to or greater than 60% by
mass, and more preferably greater than 70% by mass. In a case where
the content of the metal carbide-containing particles in the
inorganic particles is greater than 70% by mass, the curable
composition has better patterning properties.
[0053] One kind of metal carbide-containing particles may be used
singly, or two or more kinds of metal carbide-containing particles
may be used in combination. In a case where two or more kinds of
metal carbide-containing particles are used in combination, the
total content thereof is preferably within the above range. The
upper limit of the content of the metal carbide-containing
particles is not particularly limited, but is preferably equal to
or smaller than 100% by mass.
[0054] (Average Primary Particle Diameter)
[0055] The average primary particle diameter of the metal
carbide-containing particles is not particularly limited. In order
for the curable composition to have better temporal stability, the
average primary particle diameter of the metal carbide-containing
particles is preferably 1 to 300 nm, more preferably 5 to 200 nm,
even more preferably greater than 5 nm and less than 200 nm, and
particularly preferably 10 to 100 nm.
[0056] In the present specification, the average primary particle
diameter means an average primary particle diameter determined by
calculating an arithmetic mean of diameters of circles converted
from 400 metal carbide-containing particles evaluated using a
Transmission Electron Microscope (TEM). The testing method is as
described in Examples.
[0057] The metal carbide-containing particles can be manufactured
by known methods. Particularly, in view of easily obtaining the
curable composition having further improved effects of the present
invention, metal carbide-containing particles obtained by a Radio
Frequency (RF) thermal plasma method are preferable.
[0058] As the method for manufacturing metal carbide-containing
particles by the RF thermal plasma method, for example, it is
possible to use the method described in Science and Technology of
Advanced Materials 6 (2005) 111-118, "Controlling the synthesis of
TaC nanopowders by injecting liquid precursor into RF induction
plasma". The content in this document is incorporated into the
present specification.
[0059] As the element in group 5 of the periodic table that is
contained in the metal carbide-containing particles, at least one
kind of element selected from the group consisting of Ta, Nb, and V
is preferable, and Ta is more preferable.
[0060] The metal carbide-containing particles may contain an atom
other than the element in group 5 of the periodic table and carbon
(hereinafter, referred to as "impurity atom" as well). Typical
examples of the impurity atom include metal atoms other than group
5 in the periodic table and a silicon atom. In a case where the
metal carbide-containing particles contain the impurity atom, for
example, the impurity atom is typically in the form of an ion, a
metal compound (including a complex compound), an intermetallic
compound, an alloy, an oxide, a composite oxide, a nitride, an
oxynitride, a sulfide, an oxysulfide, and the like. The impurity
atom may be present as an impurity positioned between crystal
lattices or present as an amorphous impurity in the crystal grain
boundary.
[0061] The impurity atom may be intentionally added to the metal
carbide-containing particles, or may be unintentionally
incorporated into a raw material (for example, a powder raw
material of an element in group 5 of the periodic table) for
manufacturing the metal carbide-containing particles. Typically,
the impurity atom incorporated into the raw material is derived,
for example, from mineral used for manufacturing the powder raw
material.
[0062] <A2: Other Particles>
[0063] The inorganic particles may contain other particles in
addition to the metal carbide-containing particles. The content of
those other particles in the inorganic particles is equal to or
smaller than 45% by mass, preferably equal to or smaller than 40%
by mass, and more preferably less than 30% by mass. It is even more
preferable that the inorganic particles substantially do not
contain other particles. In a case where the content of other
particles in the inorganic particles is less than 30% by mass, the
curable composition has further improved patterning properties.
[0064] One kind of those other particles may be used singly, or two
or more kinds of those other particles may be used in combination.
In a case where two or more kinds of those other particles are used
in combination, the total content thereof is preferably within the
above range. The upper limit of the content of those other
particles is not particularly limited, and is preferably equal to
or smaller than 100% by mass.
[0065] As those other particles, generally, an inorganic pigment
can be used without particular limitation.
[0066] Examples of the inorganic pigment include carbon black,
silica, zinc oxide, white lead, lithopone, titanium oxide, chromium
oxide, iron oxide, precipitated barium sulfate, barite powder, red
lead, red iron oxide, chromium yellow, zinc chromium (one kind of
zinc chromium or two kinds of zinc chromium), ultramarine blue,
Prussian blue (potassium ferric ferrocyanide), zircon grey,
Praseodymium yellow, chromium titanium yellow, chromium green,
peacock, Victoria green, iron blue (irrelevant to Prussian blue),
vanadium zirconium blue, chromium tin pink, manganese pink, salmon
pink, and the like. As a black inorganic pigment, in view of
obtaining a cured film with better light blocking properties by
using the curable composition containing a small amount of the
pigment, carbon black, a metallic pigment (hereinafter, referred to
as "black pigment" as well), and the like are preferable. Examples
of the metallic pigment include a metal oxide, a metal nitride (for
example, TiN or the like), and the like containing one kind of
metallic element or two or more kinds of metallic elements selected
from the group consisting of Nb, V, Co, Cr, Cu, Mn, Ru, Fe, Ni, Sn,
Ti, and Ag.
[0067] It is preferable that the inorganic pigment contains at
least one kind of pigment selected from the group consisting of a
silver-containing metallic pigment, a tin-containing metallic
pigment, and a metallic pigment containing silver and tin. One kind
of inorganic pigment may be used singly, or two or more kinds of
inorganic pigments may be used in combination.
[0068] As the inorganic pigment, an infrared absorbing pigment can
also be used.
[0069] As the infrared absorbing pigment, a tungsten compound, a
metal boride, and the like are preferable. Among these, in order to
obtain a cured film having better light blocking properties at a
wavelength in an infrared range, a tungsten compound is preferable.
The tungsten compound is preferable because this compound more
easily transmits the wavelength in a visible range and more easily
transmits the wavelength in an absorption wavelength range of a
photopolymerization initiator (particularly, an absorption
wavelength of an oxime-based polymerization initiator).
[0070] Two or more kinds of pigments described above may be used in
combination, and a dye which will be described later may also be
used in combination. In order to adjust tint and to improve the
light blocking properties in the desired wavelength range, for
example, it is possible to adopt an aspect in which either or both
of the black pigment and the pigment having infrared blocking
properties are used in combination with a chromatic pigment of red,
green, yellow, orange, purple, and/or blue, or the like and an
aspect in which either or both of the black pigment and the
infrared blocking pigment are used in combination with a dye.
Particularly, an aspect is preferable in which either or both of
the black pigment and the infrared blocking pigment are used in
combination with a red pigment, a purple pigment, and/or a dye, and
an aspect is more preferable in which either or both of the black
pigment and the infrared blocking pigment are used in combination
with a red pigment. Furthermore, a near-infrared absorbing compound
and an infrared absorbing compound may be used in combination.
[0071] (Average Primary Particle Diameter)
[0072] The average primary particle diameter of those other
particles described above is not particularly limited. In order for
the curable composition to have better temporal stability, the
average primary particle diameter is preferably approximately the
same as that of the metal carbide-containing particles.
Specifically, the average primary particle diameter of those other
particles is preferably equal to or greater than 5 nm, more
preferably equal to or greater than 10 nm, and even more preferably
equal to or greater than 20 nm. The average primary particle
diameter of those other particles is preferably equal to or smaller
than 300 nm, more preferably equal to or smaller than 250 nm, even
more preferably equal to or smaller than 100 nm, and particularly
preferably equal to or smaller than 80 nm.
[0073] [B: Polymerizable Compound]
[0074] The curable composition contains a polymerizable compound.
In the present specification, the polymerizable compound means a
compound which contains a polymerizable group and is a component
different from the resin (a dispersant and an alkali-soluble resin)
which will be described later.
[0075] The content of the polymerizable compound in the curable
composition is not particularly limited. Generally, the content of
the polymerizable compound with respect to the total solid content
of the curable composition is preferably 5% to 40% by mass. One
kind of polymerizable compound may be used singly, or two or more
kinds of polymerizable compounds may be used in combination. In a
case where two or more kinds of polymerizable compounds are used in
combination, the total content thereof is preferably within the
above range.
[0076] The polymerizable compound is preferably a compound which
contains one or more groups containing an ethylenically unsaturated
bond, more preferably a compound which contains two or more groups
containing an ethylenically unsaturated bond, even more preferably
a compound which contains three or more groups containing an
ethylenically unsaturated bond, and particularly preferably a
compound which contains five or more groups containing an
ethylenically unsaturated bond. The upper limit of the number of
groups containing an ethylenically unsaturated bond is equal to or
smaller than 15. Examples of the group containing an ethylenically
unsaturated bond include a vinyl group, a (meth)acryl group, a
(meth)acryloyl group, and the like.
[0077] As the polymerizable compound, for example, it is possible
to use the compounds described in paragraph "0050" in
JP2008-260927A and in paragraph "0040" in JP2015-068893A. The
contents of the above paragraphs are incorporated into the present
specification.
[0078] The polymerizable compound may be in any chemical form such
as a monomer, a prepolymer, an oligomer, a mixture of these, or a
multimer of these.
[0079] The polymerizable compound is preferably a (meth)acrylate
compound having 3 to 15 functional groups, and more preferably a
(meth)acrylate compound having 5 to 15 functional groups.
[0080] As the polymerizable compound, a compound is preferable
which contains one or more groups containing an ethylenically
unsaturated bond and has a boiling point equal to or higher than
100.degree. C. under normal pressure. For example, it is possible
to use the compounds described in paragraph "0227" in
JP2013-029760A and paragraphs "0254" to "0257" in JP2008-292970A.
The contents of the above paragraphs are incorporated into the
present specification.
[0081] As the polymerizable compound, for example,
dipentaerythritol triacrylate (as a commercial product, KAYARAD
D-330; manufactured by Nippon Kayaku Co., Ltd.), dipentaerythritol
tetraacrylate (as a commercial product, KAYARAD D-320; manufactured
by Nippon Kayaku Co., Ltd.), dipentaerythritol penta(meth)acrylate
(as a commercial product, KAYARAD D-310; manufactured by Nippon
Kayaku Co., Ltd.), dipentaerythritol hexa(meth)acrylate (as a
commercial product, "KAYARAD DPHA"; a mixture with
dipentaerythritol penta(meth)acrylate, manufactured by Nippon
Kayaku Co., Ltd., corresponding to a polymerizable compound M1
which will be described later), "A-DPH-12E" (manufactured by
SHIN-NAKAMURA CHEMICAL CO., LTD.)), and a structure in which an
ethylene glycol residue or a propylene glycol residue is between
these (meth)acryloyl groups (for example, SR454 and SR499 marketed
by Sartomer) are preferable. Oligomer types of these can also be
used. In addition, NK ESTER A-TMNIT (pentaerythritol tetraacrylate,
manufactured by SHIN-NAKAMURA CHEMICAL CO., LTD.), KAYARAD RP-1040
(manufactured by Nippon Kayaku Co., Ltd., tetrafunctional,
corresponding to the polymerizable compound M3 which will be
described later), and the like can also be used.
[0082] As the polymerizable compound, for example, urethane
(meth)acrylate can also be used. The urethane (meth)acrylate is not
particularly limited, and examples of commercial products thereof
include "U-6HA", "UA-1100H", "U-6LPA", "U-15HA (having 15
functional groups, corresponding to a polymerizable compound M2
which will be described later)", "U-6H", "U-10HA", "U-10PA",
"UA-53H", and "UA-33H" (trade names) manufactured by SHIN-NAKAMURA
CHEMICAL CO. LTD "UA-306H", "UA-306T", "UA-306I", and "UA-510H"
(trade names) manufactured by KYOEISHA CHEMICAL Co., LTD, "Laromer
UA-9048", "UA-9050", and "PR9052" (trade names) manufactured by
BASF SE, "EBECRYL 220", "5129", "8301", "KRM8200", "8200AE", and
"8452" (trade names) manufactured by Daicel-Allnex Ltd., and the
like.
[0083] The polymerizable compound may contain an acid group such as
a carboxylic acid group, a sulfonic acid group, or a phosphoric
acid group. As the polymerizable compound containing an acid group,
an ester of an aliphatic polyhydroxy compound and an unsaturated
carboxylic acid is preferable, and a polymerizable compound is more
preferable which is obtained by reacting a nonaromatic carboxylic
acid anhydride with an unreacted hydroxyl group of an aliphatic
polyhydroxy compound such that an acid group is incorporated into
the compound. As the compound, the aforementioned ester in which
the aliphatic polyhydroxy compound is pentaerythritol and/or
dipentaerythritol is even more preferable.
[0084] Examples of commercial products of the polymerizable
compound include ARONIX TO-2349, M-305, M-510, and M-520
manufactured by TOAGOSEI CO., LTD., and the like.
[0085] The acid value of the polymerizable compound containing an
acid group is preferably 0.1 to 40 mgKOH/g, and more preferably 5
to 30 mgKOH/g. In a case where the acid value of the polymerizable
compound is equal to or greater than 0.1 mgKOH/g, the curable
composition has better developability (properties of being more
easily dissolved in an alkaline developer). In a case where the
acid value of the polymerizable compound is equal to or smaller
than 40 mgKOH/g, the acid value is advantageous to the
manufacturing and/or handling of the polymerizable compound, and
the polymerizable compound has better photopolymerization
properties. As a result, the curable composition has better curing
properties.
[0086] As the polymerizable compound, a compound containing a
caprolactone structure is preferable.
[0087] As the compound containing a caprolactone structure, known
compounds can be used without particular limitation as long as the
compounds contain a caprolactone structure in a molecule.
[0088] Examples of the compound containing a caprolactone structure
include .epsilon.-caprolactone-modified polyfunctional
(meth)acrylate which is obtained by esterifying a polyhydric
alcohol such as trimethylolethane, ditrimethylolethane,
trimethylolpropane, ditrimethylolpropane, pentaerythritol,
dipentaerythritol, tripentaerythritol, glycerin, diglycerol, or
trimethylol melamine, (meth)acrylic acid, and
.epsilon.-caprolactone. Particularly, a compound containing a
caprolactone structure represented by Formula (Z-1) is
preferable.
##STR00001##
[0089] In Formula (Z-1), all the six R's are groups represented by
Formula (Z-2). Alternatively, one to five R's among six R's are
groups represented by Formula (Z-2), and others are groups
represented by Formula (Z-3).
##STR00002##
[0090] In Formula (Z-2), R.sup.1 represents a hydrogen atom or a
methyl group, m represents 1 or 2, and "*" represents a binding
position.
##STR00003##
[0091] In Formula (Z-3), R.sup.1 represents a hydrogen atom or a
methyl group, and "*" represents a binding position.
[0092] The polymerizable compound containing a caprolactone
structure is marketed as a KAYARAD DPCA series from Nippon Kayaku
Co., Ltd., and examples thereof include DPCA-20 (a compound in
which m in Formulae (Z-1) to (Z-3) is 1, the number of groups
represented by Formula (Z-2) is 2, and all of R.sup.1's represent a
hydrogen atom), DPCA-30 (a compound in which m in Formulae (Z-1) to
(Z-3) is 1, the number of groups represented by Formula (Z-2) is 3,
and all of R.sup.1's represent a hydrogen atom), DPCA-60 (a
compound in which m in Formulae (Z-1) to (Z-3) is 1, the number of
groups represented by Formula (Z-2) is 6, and all of R.sup.1's
represent a hydrogen atom), DPCA-120 (a compound in which m in
Formulae (Z-1) to (Z-3) is 2, the number of groups represented by
Formula (Z-2) is 6, and all of R.sup.1's represent a hydrogen
atom), and the like.
[0093] As the polymerizable compound, a compound represented by
Formula (Z-4) or (Z-5) can also be used.
##STR00004##
[0094] In Formulae (Z-4) and (Z-5), E each independently represents
--((CH.sub.2).sub.yCH.sub.2O)-- or
--((CH.sub.2).sub.yCH(CH.sub.3)O)--, y each independently
represents an integer of 0 to 10, and X each independently
represents a (meth)acryloyl group, a hydrogen atom, or a carboxylic
acid group.
[0095] In Formula (Z-4), the total number of (meth)acryloyl groups
is 3 or 4, m each independently represents an integer of 0 to 10,
and the total number of m's is an integer of 0 to 40.
[0096] In Formula (Z-5), the total number of (meth)acryloyl groups
is 5 or 6, n each independently represents an integer of 0 to 10,
and the total number of n's is an integer of 0 to 60.
[0097] m in Formula (Z-4) is preferably an integer of 0 to 6, and
more preferably an integer of 0 to 4.
[0098] The total number of m's is preferably an integer of 2 to 40,
more preferably an integer of 2 to 16, and even more preferably an
integer of 4 to 8.
[0099] n in Formula (Z-5) is preferably an integer of 0 to 6, and
more preferably an integer of 0 to 4.
[0100] The total number of n's is preferably an integer of 3 to 60,
more preferably an integer of 3 to 24, and even more preferably an
integer of 6 to 12.
[0101] It is preferable that a terminal on the oxygen atom side of
--((CH.sub.2).sub.yCH.sub.2O)-- or
--((CH.sub.2).sub.yCH(CH.sub.3)O)-- in Formula (Z-4) or Formula
(Z-5) is bonded to X.
[0102] One kind of compound represented by Formula (Z-4) or Formula
(Z-5) may be used singly, or two or more kinds of compounds
represented by Formula (Z-4) or Formula (Z-5) may be used in
combination. Particularly, an aspect is preferable in which all of
six X's in Formula (Z-5) are acryloyl groups. Furthermore, it is
preferable to use the compound represented by Formula (Z-5), in
which all of six X's are acryloyl groups, in combination with the
compound represented by Formula (Z-5) in which at least one of six
X's is a hydrogen atom. The curable composition containing the
above compound has better developability.
[0103] The total content of the compound represented by Formula
(Z-4) or Formula (Z-5) in the polymerizable compound is preferably
equal to or greater than 20% by mass, and more preferably equal to
or greater than 50% by mass.
[0104] Among the compounds represented by Formula (Z-4) or Formula
(Z-5), either or both of a pentaerythritol derivative and a
dipentaerythritol derivative are more preferable.
[0105] The polymerizable compound may contain a cardo-skeleton.
[0106] As the polymerizable compound containing a cardo-skeleton, a
polymerizable compound containing a 9,9-bisarylfluorene skeleton is
preferable.
[0107] The polymerizable compound containing a cardo-skeleton is
not particularly limited, and examples thereof include an ONCOAT EX
series (manufactured by NAGASE & CO., LTD.), OGSOL
(manufactured by Osaka Gas Chemicals Co., Ltd.), and the like.
[0108] [C: Polymerization Initiator]
[0109] The curable composition contains a polymerization
initiator.
[0110] As the polymerization initiator, known polymerization
initiators can be used without particular limitation. Examples of
the polymerization initiator include a photopolymerization
initiator, a thermal polymerization initiator, and the like. Among
these, a photopolymerization initiator is preferable. It is also
preferable that the polymerization initiator is selected from a
polymerization initiator without colorability and a polymerization
initiator having high fading properties. As the polymerization
initiator, a so-called radical polymerization initiator is
preferable.
[0111] The content of the polymerization initiator in the curable
composition is not particularly limited, but is preferably 0.5% to
20% by mass with respect to the total solid content of the curable
composition in general. One kind of polymerization initiator may be
used singly, or two or more kinds of polymerization initiators may
be used in combination. In a case where two or more kinds of
polymerization initiators are used in combination, the total
content thereof is preferably within the above range.
[0112] Examples of the thermal polymerization initiator include an
azo compound such as 2,2'-azobisisobutyronitrile (AIBN),
3-carboxypropionitrile, azobismalenonitrile, or
dimethyl-(2,2')-azobis(2-methylpropionate) [V-601] and an organic
peroxide such as benzoyl peroxide, lauroyl peroxide, or potassium
peroxide.
[0113] Examples of the thermal polymerization initiator include the
compounds described in "Ultraviolet Curing System", SOGO GIJUTSU
CENTER, 1989, pp. 65-148, and the like.
[0114] <Photopolymerization Initiator>
[0115] It is preferable that the curable composition contains a
photopolymerization initiator.
[0116] As the photopolymerization initiator, known
photopolymerization initiators can be used without particular
limitation as long as they can initiate the polymerization of a
polymerizable compound. As the photopolymerization initiator, for
example, a compound exhibiting photosensitivity in a range of
ultraviolet rays to visible rays is preferable. Furthermore, the
photopolymerization initiator may be an activator which generates
active radicals by interacting in a certain way with a photoexcited
sensitizer or an initiator which initiates cationic polymerization
according to the type of the polymerizable compound.
[0117] Furthermore, it is preferable that the curable composition
contains, as a photopolymerization initiator, at least one kind of
compound having at least a molar absorption coefficient which is
approximately 50 in a range of about 300 to 800 nm (more preferably
330 to 500 nm).
[0118] The content of the photopolymerization initiator in the
curable composition is not particularly limited, but is preferably
0.5% to 20% by mass with respect to the total solid content of the
curable composition in general. One kind of photopolymerization
initiator may be used singly, or two or more kinds of
photopolymerization initiators may be used in combination. In a
case where two or more kinds of photopolymerization initiators are
used in combination, the total content thereof is preferably within
the above range.
[0119] Examples of the photopolymerization initiator include a
halogenated hydrocarbon derivative (for example, a halogenated
hydrocarbon derivative containing a triazine skeleton, a
halogenated hydrocarbon derivative containing an oxadiazole
skeleton, or the like), an acyl phosphine compound such as acyl
phosphine oxide, hexaaryl biimidazole, an oxime compound such as an
oxime derivative, an organic peroxide, a thio compound, a ketone
compound, an aromatic onium salt, an aminoacetophenone compound,
hydroxyacetophenone, and the like.
[0120] Regarding the photopolymerization initiator, for example,
paragraphs "0265" to "0268" in JP2013-029760A can be referred to,
and the contents of the paragraphs are incorporated into the
present specification.
[0121] More specifically, as the photopolymerization initiator, for
example, the aminoacetophenone-based initiator described in
JP1998-291969A (JP-H10-291969A) and the acyl phosphine-based
initiator described in JP4225898B can be used. The contents of the
above documents are incorporated into the present
specification.
[0122] As the hydroxyacetophenone compound, for example, it is
possible to use IRGACURE-184, DAROCUR-1173, IRGACURE-500,
IRGACURE-2959, and IRGACURE-127 (trade names: manufactured by BASF
SE), but the present invention is not limited to these.
[0123] As the aminoacetophenone compound, for example, it is
possible to use commercial products such as IRGACURE-907,
IRGACURE-369, and IRGACURE-379EG (trade names: manufactured by BASF
SE), but the present invention is not limited to these. As the
aminoacetophenone compound, it is also possible to use the compound
described in JP2009-191179A whose absorption wavelength is matched
with a light source of a long wavelength such as 365 nm, 405 nm, or
the like. The content of the above document is incorporated into
the present specification.
[0124] As the acyl phosphine compound, IRGACURE-819 and
IRGACURE-TPO (trade names: manufactured by BASF SE), and the like
can be used.
[0125] (Oxime Compound)
[0126] As the photopolymerization initiator, an oxime ester-based
polymerization initiator (oxime ester compound, hereinafter,
referred to as "oxime compound" as well) is preferable. The oxime
compound has higher sensitivity and higher polymerization
efficiency. Consequently, even in a case where the curable
composition containing the oxime compound contains a large amount
of pigments, the curable composition has better curing
properties.
[0127] As the oxime compound, it is possible to use the compound
described in JP2001-233842A, the compound described in
JP2000-080068A, and the compound described in JP2006-342166A. The
contents of the above documents are incorporated into the present
specification.
[0128] Examples of the oxime compound include
3-benzoyloxyiminobutan-2-one, 3-aceotxyiminobutan-2-one,
3-propionyloxyiminobutane-2-one, 2-acetoxyiminopentan-3-one,
2-acetoxyimino-1-phenylpropan-1-one,
2-benzoyloxyimino-1-phenylpropan-1-one,
3-(4-toluenesulfonyloxy)iminobutan-2-one,
2-ethoxycarbonyloxyimino-1-phenylpropan-1-one, and the like.
[0129] Examples of the oxime compound also include the compounds
described in J. C. S. Perkin II (1979) pp. 1653-1660, J. C. S.
Perkin II (1979) pp. 156-162, Journal of Photopolymer Science and
Technology (1995) pp. 202-232, JP2000-066385A, JP2000-080068A,
JP2004-534797A, and JP2006-342166A, and the like. The contents of
the above documents are incorporated into the present
specification.
[0130] Examples of commercial products of the oxime compound
include IRGACURE-OXE01 (manufactured by BASF SE), IRGACURE-OXE02
(manufactured by BASF SE), IRGACURE-OXE03 (manufactured by BASF
SE), or IRGACURE-OXE04 (manufactured by BASF SE), TR-PBG-304
(manufactured by TRONLY), ADEKA ARKLS NCI-831 and ADEKA ARKLS
NCI-930 (manufactured by ADEKA CORPORATION), N-1919 (carbazoleoxime
ester skeleton-containing photoinitiator (manufactured by ADEKA
CORPORATION)), NCI-730 (manufactured by ADEKA CORPORATION), and the
like.
[0131] As oxime compounds other than the above, the compound
described in JP2009-519904A in which oxime is linked to N-position
of carbazole; the compound described in U.S. Pat. No. 7,626,957B in
which a hetero substituent is introduced into a benzophenone
moiety; the compound described in JP2010-015025A and US2009/292039A
in which a nitro group is introduced into the moiety of a coloring
agent; the ketoxime compound described in WO2009/131189A; the
compound described in U.S. Pat. No. 7,556,910B that contains a
triazine skeleton and an oxime skeleton in the same molecule; the
compound described in JP2009-221114A that has absorption maximum
wavelength at 405 nm and exhibits excellent sensitivity with
respect to a light source of g-line; and the like may also be
used.
[0132] Furthermore, the compounds described in paragraphs "0274"
and "0275" in JP2013-029760A can also be used, and the contents of
these paragraphs are incorporated into the present
specification.
[0133] As the oxime compound, a compound containing a structure
represented by Formula (OX-1) is preferable. In the oxime compound,
the N--O bond may be an (E) isomer or a (Z) isomer. As the oxime
compound, the (E) isomer and the (Z) isomer may be used in
combination.
##STR00005##
[0134] In Formula (OX-1), R and B each independently represent a
monovalent substituent, A represents a divalent organic group, and
Ar represents an aryl group.
[0135] As the monovalent substituent represented by R in Formula
(OX-1), a group of monovalent nonmetallic atoms is preferable.
[0136] Examples of the group of monovalent nonmetallic atoms
include an alkyl group, an aryl group, an acyl group, an
alkoxycarbonyl group, an aryloxycarbonyl group, a heterocyclic
group, an alkylthiocarbonyl group, an arylthiocarbonyl group, and
the like. These groups may have one or more substituents.
Furthermore, each of the substituents may be further substituted
with another substituent.
[0137] Examples of the substituent include a halogen atom, an
aryloxy group, an alkoxycarbonyl group, an aryloxycarbonyl group,
an acyloxy group, an acyl group, an alkyl group, an aryl group, and
the like.
[0138] As the monovalent substituent represented by B in Formula
(OX-1), an aryl group, a heterocyclic group, an arylcarbonyl group,
or a heterocyclic carbonyl group is preferable, and an aryl group
or a heterocyclic group is more preferable. These groups may have
one or more substituents. Examples of the substituents are the same
as the examples of the aforementioned substituents.
[0139] As the divalent organic group represented by A in Formula
(OX-1), an alkylene group having 1 to 12 carbon atoms, a
cycloalkylene group, or an alkynylene group is preferable. These
groups may have one or more substituents. Examples of the
substituents include the substituents described above.
[0140] As the photopolymerization initiator, a fluorine
atom-containing oxime compound can also be used. Specific examples
of the fluorine atom-containing oxime compound include the compound
described in JP2010-262028A; the compounds 24 and 36 to 40
described in JP2014-500852A; the compound (C-3) described in
JP2013-164471A; and the like. The contents of the above documents
are incorporated into the present specification.
[0141] As the photopolymerization initiator, compounds represented
by Formulae (1) to (4) can also be used.
##STR00006##
[0142] In Formula (1), R.sup.1 and R.sup.2 each independently
represent an alkyl group having 1 to 20 carbon atoms, an alicyclic
hydrocarbon group having 4 to 20 carbon atoms, an aryl group having
6 to 30 carbon atoms, or an aryl alkyl group having 7 to 30 carbon
atoms. In a case where each of R.sup.1 and R.sup.2 each represent a
phenyl group, the phenyl groups may form a fluorene group by being
bonded to each other. R.sup.3 and R.sup.4 each independently
represent a hydrogen atom, an alkyl group having 1 to 20 carbon
atoms, an aryl group having 6 to 30 carbon atoms, an aryl alkyl
group having 7 to 30 carbon atoms, or a heterocyclic group having 4
to 20 carbon atoms, and X represents a direct bond or a carbonyl
group.
[0143] R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in Formula (2) have
the same definition as R.sup.1, R.sup.2, R.sup.3, and R.sup.4 in
Formula (1). R.sup.5 represents --R.sup.6, --OR.sup.6, --SR.sup.6,
--COR.sup.6, --CONR.sup.6R.sup.6, --NR.sup.6COR.sup.6,
--OCOR.sup.6, --COOR.sup.6, --SCOR.sup.6, --OCSR.sup.6,
--COSR.sup.6, --CSOR.sup.6, --CN, a halogen atom, or a hydroxyl
group, R.sup.6 represents an alkyl group having 1 to 20 carbon
atoms, an aryl group having 6 to 30 carbon atoms, an aryl alkyl
group having 7 to 30 carbon atoms, or a heterocyclic group having 4
to 20 carbon atoms, X represents a direct bond or a carbonyl group,
and a represents an integer of 0 to 4.
[0144] In Formula (3), R.sup.1 represents an alkyl group having 1
to 20 carbon atoms, an alicyclic hydrocarbon group having 4 to 20
carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl
alkyl group having 7 to 30 carbon atoms, R.sup.3 and R.sup.4 each
independently represent a hydrogen atom, an alkyl group having 1 to
20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aryl
alkyl group having 7 to 30 carbon atoms, or a heterocyclic group
having 4 to 20 carbon atoms, and X represents a direct bond or a
carbonyl group.
[0145] R.sup.1, R.sup.3, and R.sup.4 in Formula (4) have the same
definition as R.sup.1, R.sup.3, and R.sup.4 in Formula (3). R.sup.5
represents --R.sup.6, --OR.sup.6, --SR.sup.6, --COR.sup.6,
--CONR.sup.6R.sup.6, --NR.sup.6COR.sup.6, --OCOR.sup.6,
--COOR.sup.6, --SCOR.sup.6, --OCSR.sup.6, --COSR.sup.6,
--CSOR.sup.6, --CN, a halogen atom, or a hydroxyl group, R.sup.6
represents an alkyl group having 1 to 20 carbon atoms, an aryl
group having 6 to 30 carbon atoms, an aryl alkyl group having 7 to
30 carbon atoms, or a heterocyclic group having 4 to 20 carbon
atoms, X represents a direct bond or a carbonyl group, and a
represents an integer of 0 to 4.
[0146] In Formula (1) and Formula (2), R.sup.1 and R.sup.2
preferably each independently represent a methyl group, an ethyl
group, a n-propyl group, an i-propyl group, a cyclohexyl group, or
a phenyl group. R.sup.3 preferably represents a methyl group, an
ethyl group, a phenyl group, a tolyl group, or a xylyl group.
R.sup.4 preferably represents an alkyl group having 1 to 6 carbon
atoms or a phenyl group. R.sup.5 preferably represents a methyl
group, an ethyl group, a phenyl group, a tolyl group, or a naphthyl
group. X preferably represents a direct bond.
[0147] In Formula (3) and Formula (4), R.sup.1 preferably each
independently represents a methyl group, an ethyl group, a n-propyl
group, an i-propyl group, a cyclohexyl group, or a phenyl group.
R.sup.3 preferably represents a methyl group, an ethyl group, a
phenyl group, a tolyl group, or a xylyl group. R.sup.4 preferably
represents an alkyl group having 1 to 6 carbon atoms or a phenyl
group. R.sup.5 preferably represents a methyl group, an ethyl
group, a phenyl group, a tolyl group, or a naphthyl group. X
preferably represents a direct bond.
[0148] Specific examples of the compounds represented by Formula
(1) and Formula (2) include the compounds described in paragraphs
"0076" to "0079" in JP2014-137466A, and the contents of the
paragraphs are incorporated into the present specification.
[0149] Specific examples of oxime compounds preferably used in the
curable composition will be shown below. As the oxime compounds,
the compounds described in Table 1 in WO2015/036910A can also be
used, and the content of the document is incorporated into the
present specification.
##STR00007## ##STR00008## ##STR00009## ##STR00010##
[0150] The oxime compound has a maximum absorption wavelength
preferably in a range of a wavelength of 350 to 500 nm, and more
preferably in a range of a wavelength of 360 to 480 nm. As the
oxime compound, a compound having a high absorbance at 365 nm and
405 nm is even more preferable.
[0151] From the viewpoint of sensitivity, a molar absorption
coefficient of the oxime compound at 365 nm or 405 nm is preferably
1,000 to 300,000, more preferably 2,000 to 300,000, and even more
preferably 5,000 to 200,000.
[0152] The molar absorption coefficient of a compound can be
measured by known methods. For example, it is preferable that the
molar absorption coefficient is measured using an
ultraviolet/visible spectrophotometer (Cary-5 spectrophotometer
manufactured by Varian, Inc.) and an ethyl acetate solvent at a
concentration of 0.01 g/L.
[0153] If necessary, two or more kinds of photopolymerization
initiators may be used in combination.
[0154] As the photopolymerization initiator, it is also possible to
use the compounds described in paragraph "0052" in JP2008-260927A,
paragraphs "0033" to "0037" in JP2010-097210A, and paragraph "0044"
in JP2015-068893A, and the contents of the above paragraphs are
incorporated into the present specification.
[0155] [Optional Components]
[0156] The curable composition may contain other components as long
as the curable composition brings about the effects of the present
invention. Examples of those other components include a resin, a
polymerization inhibitor, a solvent, a colorant, a surfactant, and
the like. Hereinafter, the optional components incorporated into
the curable composition will be specifically described.
[0157] <D: Polymerization Inhibitor>
[0158] It is preferable that the curable composition contains a
polymerization inhibitor. In a case where the curable composition
contains a polymerization inhibitor, it is possible to inhibit the
polymerizable compound in the curable composition from being
unintentionally polymerized. Therefore, the curable composition has
better temporal stability. Furthermore, because the unintended
polymerization of the polymerizable compound in the curable
composition is inhibited, the curable composition has better
patterning properties.
[0159] As the polymerization inhibitor, known polymerization
inhibitors can be used without particular limitation. Examples of
the polymerization inhibitor include a phenol-based polymerization
inhibitor (for example, p-methoxyphenol,
2,5-di-tert-butyl-4-methylphenol, 2,6-di-tert-butyl-4-methylphenol,
4,4'-thiobis(3-methyl-6-t-butylphenol),
2,2'-methylenebis(4-methyl-6-t-butylphenol), 4-methoxynaphthaol, or
the like), a hydroquinone-based polymerization inhibitor (for
example, hydroquinone, 2,6-di-tert-butylhydroquinone, or the like);
a quinone-based polymerization inhibitor (for example, benzoquinone
or the like), a free radical-based polymerization inhibitor (for
example, a 2,2,6,6-tetramethylpiperidin-1-oxyl free radical, a
4-hydroxy-2,2,6,6-tetramethylpiperidin-1-oxyl free radical, or the
like); a nitrobenzene-based polymerization inhibitor (for example,
nitrobenzene, 4-nitrotoluene, or the like); a phenothiazine-based
polymerization inhibitor (for example, phenothiazine,
2-methoxyphenothiazine, or the like); and the like.
[0160] Among these, in order for the curable composition to have
further improved effects of the present invention, a phenol-based
polymerization inhibitor or a free radical-based polymerization
inhibitor is preferable.
[0161] The polymerization inhibitor may be mixed with other
components at the time of preparing the curable composition.
Alternatively, the polymerization initiator used at the time of
synthesizing the aforementioned resin and the like may be mixed
with other components together with the resin.
[0162] The content of the polymerization inhibitor in the curable
composition is not particularly limited. In order for the curable
composition to have better temporal stability and better patterning
properties, the content of the polymerization inhibitor with
respect to the total solid content of the curable composition is
preferably 0.00001% to 1% by mass.
[0163] One kind of polymerization inhibitor may be used singly, or
two or more kinds of polymerization inhibitors may be used in
combination. In a case where two or more kinds of polymerization
inhibitors are used in combination, the total content thereof is
preferably within the above range.
[0164] The effect of the polymerization inhibitor becomes apparent
in a case where the polymerization inhibitor is used together with
a resin containing curable group. For example, even in a case where
it is concerned that the resin containing a curable group may be
polymerized due to the increase in temperature of a dispersion
composition and/or the curable composition in the process of
preparing the dispersion composition; after the preparation of the
dispersion composition; in the process of preparing the curable
composition; after the preparation of the curable composition; and
the like or due to the long-term storage, the polymerization
inhibitor can be used without any problem.
[0165] <E: Resin>
[0166] It is preferable that the curable composition contains a
resin. Examples of the resin include a dispersant, an
alkali-soluble resin, and the like.
[0167] The content of the resin in the curable composition is not
particularly limited. In order for the curable composition to have
better patterning properties, the content of the resin with respect
to the total solid content of the curable composition is preferably
equal to or greater than 5% by mass, more preferably equal to or
greater than 10% by mass, even more preferably equal to or greater
than 15% by mass, and particularly preferably equal to or greater
than 18% by mass. In order for the curable composition to have
better patterning properties, the upper limit of the content of the
resin is preferably equal to or smaller than 45% by mass, more
preferably equal to or smaller than 40% by mass, and even more
preferably less than 40% by mass.
[0168] One kind of resin may be used singly, or two or more kinds
of resins may be used in combination. In a case where two or more
kinds of resins are used in combination, the total content thereof
is preferably within the above range.
[0169] (E1: Dispersant)
[0170] It is preferable that the curable composition contains a
dispersant (corresponding to a resin). In the present
specification, a dispersant means a compound different from the
alkali-soluble resin which will be described later.
[0171] The content of the dispersant in the curable composition is
not particularly limited. In order for the curable composition to
have better temporal stability and better patterning properties,
the content of the dispersant with respect to the total solid
content of the curable composition is preferably equal to or
greater than 5% by mass, and more preferably equal to or greater
than 6% by mass. The upper limit of the content of the dispersant
is not particularly limited, but is preferably equal to or smaller
than 40% by mass and more preferably equal to or smaller than 35%
by mass in general.
[0172] One kind of dispersant may be used singly, or two or more
kinds of dispersants may be used in combination. In a case where
two or more kinds of dispersants are used in combination, the total
content thereof is preferably within the above range.
[0173] As the dispersant, known dispersants can be used without
particular limitation.
[0174] Examples of the dispersant include a polymer dispersant.
Examples of the polymer dispersant include polyamide amine and a
salt thereof, polycarboxylic acid and a salt thereof, a
high-molecular-weight unsaturated acid ester, modified
polyurethane, modified polyester, modified poly(meth)acrylate, a
(meth)acrylic copolymer, a naphthalenesulfonic acid formalin
condensate, and the like.
[0175] Furthermore, as the dispersant, a polyoxyethylene alkyl
phosphoric acid ester, polyoxyethylene alkyl amine, a pigment
derivative, and the like can be used.
[0176] Among these, a polymer compound is preferred as the
dispersant. The polymer compound can be further classified into a
linear polymer, a terminal-modified polymer, a graft polymer, and a
block polymer based on the structure.
[0177] (Polymer Compound)
[0178] The polymer compound functions to prevent the reaggregation
of a substance to be dispersed by being adsorbed onto the surface
of inorganic particles (containing metal carbide-containing
particles, hereinafter, referred to as "pigment" in some cases).
Therefore, as the polymer compound, a terminal-modified polymer, a
graft polymer (containing a polymer chain), and a block polymer are
preferable which contain a moiety anchored to the pigment
surface.
[0179] It is preferable that the polymer compound contains a
structural unit containing a graft chain. In the present
specification, "structural unit" has the same definition as
"repeating unit".
[0180] The polymer compound which contains the structural unit
containing a graft chain exhibits higher affinity with a solvent.
Because the polymer compound which contains a structural unit
containing a graft chain exhibits higher affinity with a solvent,
the polymer compound more easily disperses the pigment and the like
and makes it more difficult for the initial dispersion state to
change even after the lapse of time after the pigment and the like
are dispersed (the polymer compound has better temporal stability).
In addition, because the polymer compound which contains a
structural unit containing a graft chain contains a graft chain,
the polymer compound exhibits higher affinity with the
polymerizable compound, which will be described later, and/or other
components and the like. Consequently, at the time of alkali
development which will be described later, the polymer compound
which contains a structural unit containing a graft chain hardly
generates residues resulting from an unreacted polymerizable
compound and the like.
[0181] The longer the graft chain (the larger the formula weight),
the stronger the steric repulsion effect, and hence the
dispersibility of the pigment and the like is improved. In
contrast, in a case where the graft chain is too long, the
adsorptivity with respect to the pigment and the like is reduced,
and hence the dispersibility of the pigment and the like tends to
be reduced. Therefore, the number of atoms (except for hydrogen
atoms) constituting the graft chain is preferably 40 to 10,000,
more preferably 50 to 2,000, and even more preferably 60 to
500.
[0182] Herein, the graft chain means a portion from the base of a
main chain of the polymer compound (an atom bonded to the main
chain in a group which is branched off the main chain) to the
terminal of a group branching off the main chain.
[0183] As the graft chain, a polymer chain containing a polymer
structure is preferable. The polymer structure that the polymer
chain contains is not particularly limited, and examples thereof
include a poly(meth)acrylate structure (for example, a
poly(meth)acryl structure), a polyester structure, a polyurethane
structure, a polyurea structure, a polyamide structure, a polyether
structure, and the like.
[0184] In order for higher affinity to be exhibited with a polymer
chain and a solvent and for the polymer compound to more easily
disperse the pigment and the like, the polymer chain preferably
contains at least one kind of structure selected from the group
consisting of a polyester structure, a polyether structure, and a
poly(meth)acrylate structure, and more preferably contains at least
one kind of structure selected from the group consisting of a
polyester structure and a polyether structure.
[0185] As the polyester structure and the polyether structure that
the polymer chain has, the following aspects are preferable.
##STR00011##
[0186] In the above formulae, R.sup.1 in Formula (GF1) represents
an alkylene group, and n represents 0 or 1. In Formula (GF2),
R.sup.2 represents an alkylene group different from R.sup.1, and m
represents 0 or 1. In Formula (GF3), R.sup.3 represents an alkyl
group.
[0187] In order for the curable composition to have better temporal
stability, it is preferable that the polymer chain contains at
least one kind of structural unit selected from the group
consisting of the structural unit represented by Formula (GF1) and
the structural units represented by Formula (GF2) and Formula (GF3)
among the above.
[0188] A macromonomer containing the aforementioned polymer chain
(a monomer which contains a polymer structure and constitutes a
graft chain by being bonded to the main chain of a polymer compound
(for example, a copolymer)) is not particularly limited, and is
preferably a macromonomer containing a reactive double bond
group.
[0189] Examples of commercial macromonomers, which correspond to
the structural unit containing a polymer chain contained in the
polymer compound and can be used for synthesizing the polymer
compound, include AA-6, AA-10, AB-6, AS-6, AN-6, AW-6, AA-714,
AY-707, AY-714, AK-5, AK-30, and AK-32 (trade names, manufactured
by TOAGOSEI CO., LTD.); BLEMMER PP-100, BLEMMER PP-500, BLEMMER
PP-800, BLEMMER PP-1000, BLEMMER 55-PET-800, BLEMMER PME-4000,
BLEMMER PSE-400, BLEMMER PSE-1300, and BLEMMER 43PAPE-600B (trade
names, manufactured by NOF CORPORATION); and the like.
[0190] The aforementioned dispersant preferably contains at least
one kind of structure selected from the group consisting of
polymethyl acrylate, polymethyl methacrylate, and cyclic or linear
polyester, more preferably contains at least one kind of structure
selected from the group consisting of polymethyl acrylate,
polymethyl methacrylate, and linear polyester, and even more
preferably contains at least one kind of structure selected from
the group consisting of a polymethyl acrylate structure, a
polymethyl methacrylate structure, a polycaprolactone structure,
and a polyvalerolactone structure.
[0191] The dispersant may contain only one kind of the
aforementioned structure in a molecule or plural kinds of the
aforementioned structures in a molecule.
[0192] The polycaprolactone structure refers to a structure
containing a structure, which is obtained by ring opening of
.epsilon.-caprolactone, as a repeating unit. The polyvalerolactone
structure refers to a structure containing a structure, which is
obtained by ring opening of .delta.-valerolactone, as a repeating
unit.
[0193] Examples of the dispersant containing the polycaprolactone
structure include a compound represented by Formula (1) or Formula
(2) in which j or k each represents 5. Examples of the dispersant
containing the polyvalerolactone structure include a compound
represented by Formula (1) or Formula (2) in which j or k each
represents 4.
[0194] Examples of the dispersant containing a polymethyl acrylate
structure include a compound represented by Formula (4) in which
X.sup.5 represents a hydrogen atom and R.sup.4 represents a methyl
group.
[0195] Examples of the dispersant containing a polymethyl
methacrylate structure include a compound represented by Formula
(4) in which X.sup.5 represents a methyl group and R.sup.4
represents a methyl group.
[0196] Structural Unit Containing Graft Chain
[0197] As the structural unit containing a graft chain that the
polymer compound contains, at least one kind of polymer
chain-containing structural unit selected from the group consisting
of Formula (1) to Formula (4) is preferable, and at least one kind
of polymer chain-containing structural unit selected from the group
consisting of Formula (1A), Formula (2A), Formula (3A), Formula
(3B), and Formula (4) is more preferable.
##STR00012##
[0198] In Formula (1) to Formula (4), W.sup.1, W.sup.2, W.sup.3,
and W.sup.4 each independently represent an oxygen atom or NH. Each
of W.sup.1, W.sup.2, W.sup.3, and W.sup.4 is preferably an oxygen
atom.
[0199] In Formula (1) to Formula (4), X.sup.1, X.sup.2, X.sup.3,
X.sup.4, and X.sup.5 each independently represent a hydrogen atom
or a monovalent organic group. From the viewpoint of the
restriction on synthesis, X.sup.1, X.sup.2, X.sup.3, X.sup.4, and
X.sup.5 preferably each independently represent a hydrogen atom or
an alkyl group having 1 to 12 carbon atoms, more preferably each
independently represent a hydrogen atom or a methyl group, and even
more preferably each independently represent a methyl group.
[0200] In Formula (1) to Formula (4), Y.sup.1, Y.sup.2, Y.sup.3,
and Y.sup.4 each independently represent a divalent linking group.
The structure of the linking group is not particularly limited.
Examples of the divalent linking groups represented by Y.sup.1,
Y.sup.2, Y.sup.3, and Y.sup.4 include linking groups represented by
Formulae (Y-1) to (Y-21), and the like. In Formulae (Y-1) to
(Y-21), A and B mean moieties bonded to the left terminal group and
the right terminal group in Formula (1) to Formula (4)
respectively. Among the following structures, in view of the
simplicity of synthesis, (Y-2) or (Y-13) is more preferable.
##STR00013## ##STR00014## ##STR00015##
[0201] In Formula (1) to Formula (4), Z.sup.1, Z.sup.2, Z.sup.3,
and Z.sup.4 each independently represent a monovalent organic
group. The structure of the organic group is not particularly
limited. Examples of the organic group include an alkyl group, a
hydroxyl group, an alkoxy group, an aryloxy group, a heteroaryloxy
group, an alkyl thioether group, an aryl thioether group, a
heteroaryl thioether group, an amino group, and the like.
[0202] Particularly, in view of more easily dispersing the pigment
and the like, it is preferable that the organic groups represented
by Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 have a steric repulsion
effect. Z.sup.1, Z.sup.2, Z.sup.3, and Z.sup.4 more preferably each
independently represent an alkyl group or alkoxy group having 5 to
24 carbon atoms, and even more preferably each independently
represent a branched alkyl group having 5 to 24 carbon atoms, a
cyclic alkyl group having 5 to 24 carbon atoms, or an alkoxy group
having 5 to 24 carbon atoms. The alkyl group contained in the
alkoxy group may be any of a linear, branched, or cyclic alkyl
group.
[0203] As the monovalent organic group represented by Z.sup.1,
Z.sup.2, Z.sup.3, and Z.sup.4 in Formula (1) to Formula (4), in
order for the curable composition to have better temporal
stability, a curable group-containing group is preferable. The
curable group-containing group is not particularly limited, and
examples thereof include a group represented by -L.sup.CR-R.sup.CR.
R.sup.CR represents the following curable group, and -L.sup.CR-
represents a divalent linking group having 1 to 20 carbon atoms
that may contain a nitrogen atom and/or an oxygen atom.
[0204] Examples of the curable group include an ethylenically
unsaturated group (for example, a (meth)acryloyl group, a vinyl
group, a styryl group, or the like), a cyclic ether group (for
example, an epoxy group, an oxetanyl group, or the like), and the
like, but the present invention is not limited to these. In view of
making it possible to control the polymerization by a radical
reaction, as the curable group, an ethylenically unsaturated group
is preferable. As the ethylenically unsaturated group, a
(meth)acryloyl group is particularly preferable.
[0205] In Formula (1) to Formula (4), n, m, p, and q each
independently represent an integer of 1 to 500.
[0206] In Formula (1) and Formula (2), j and k each independently
represent an integer of 2 to 8.
[0207] In Formula (1) and Formula (2), in order for the curable
composition to have better temporal stability and better
developability, j and k preferably each represent an integer of 4
to 6, and more preferably each represent 5.
[0208] In Formula (1) and Formula (2), n and m preferably each
represent an integer equal to or greater than 10, and more
preferably each represent an integer equal to or greater than
20.
[0209] In Formula (1), a plurality of units each represented by
"--O--C.sub.jH.sub.2j--C(.dbd.O)--" may be the same as or different
from each other, and in Formula (2), a plurality of units each
represented by "--O--C(.dbd.O)--C.sub.kH.sub.2k--" may be the same
as or different from each other. That is, in a case where a
plurality of units each represented by
"--O--C.sub.jH.sub.2j--C(.dbd.O)--" are different from each other,
and a plurality of units each represented by
"--O--C(.dbd.O)--C.sub.kH.sub.2k--" are different from each other,
these may be bonded to each other in the form of a random
copolymer, an alternating copolymer, or a block copolymer. However,
in order for the curable composition to have better temporal
stability, a block copolymer is preferable.
[0210] In Formula (3), R.sup.3 represents a branched or linear
alkylene group. R.sup.3 is preferably an alkylene group having 1 to
10 carbon atoms, and more preferably an alkylene group having 2 or
3 carbon atoms. In a case where p is 2 to 500, a plurality of
R.sup.3's may be the same as or different from each other.
[0211] In Formula (4), R.sup.4 represents a hydrogen atom or a
monovalent organic group. The structure of the monovalent organic
group is not particularly limited. As R.sup.4, for example, a
hydrogen atom, an alkyl group, an aryl group, or a heteroaryl group
is preferable, and a hydrogen atom or an alkyl group is more
preferable.
[0212] In a case where R.sup.4 represents an alkyl group, as the
alkyl group, a linear alkyl group having 1 to 20 carbon atoms, a
branched alkyl group having 3 to 20 carbon atoms, or a cyclic alkyl
group having 5 to 20 carbon atoms is preferable, a linear alkyl
group having 1 to 20 carbon atoms is more preferable, and a linear
alkyl group having 1 to 6 carbon atoms is even more preferable. In
a case where q in Formula (4) is 2 to 500, a plurality of X.sup.5's
and a plurality of R.sup.4's in the structural unit containing a
graft chain may be the same as or different from each other
respectively.
[0213] The polymer compound may contain two or more kinds of graft
chain-containing structural units having different structures. That
is, the polymer compound may contain structural units represented
by Formula (1) to Formula (4) having different structures in a
molecule. Furthermore, in a case where n, m, p, and q in Formula
(1) to Formula (4) each represent an integer equal to or greater
than 2, the compounds represented by Formula (1) and Formula (2)
may contain structures, in which j and k represent different
numbers, in a side chain, and a plurality of R.sup.3's, R.sup.4's,
and X.sup.5's in molecules of the compounds represented by Formula
(3) and Formula (4) may be the same as or different from each
other.
[0214] As the structural unit represented by Formula (1), in order
for the curable composition to have better temporal stability and
better developability, a structural unit represented by Formula
(1A) is more preferable.
[0215] Furthermore, as the structural unit represented by Formula
(2), in order for the curable composition to have better temporal
stability and developability, a structural unit represented by
Formula (2A) is more preferable.
##STR00016##
[0216] X.sup.1, Y.sup.1, Z.sup.1, and n in Formula (1A) are the
same as X.sup.1, Y.sup.1, Z.sup.1, and n in Formula (1) described
above. X.sup.2, Y.sup.2, Z.sup.2, and m in Formula (2A) are the
same as X.sup.2, Y.sup.2, Z.sup.2, and m in Formula (2) described
above.
[0217] As the structural unit represented by Formula (1), a
structural unit represented by Formula (A1) is also preferable.
##STR00017##
[0218] In Formula A1, R.sup.1 represents a hydrogen atom or an
alkyl group, X.sup.1 represents a single bond or a divalent linking
group, L.sup.1 and L.sup.2 may be the same as or different from
each other and each represent at least one kind of structural unit
selected from the group consisting of Formula (GF1), Formula (GF2),
and Formula (GF3), p and q each represents an integer equal to or
greater than 1, and Z.sup.1 represents a group containing the
curable group described above.
[0219] In order for the curable composition to have better temporal
stability and better developability, as the structural unit
represented by Formula (3), a structural unit represented by
Formula (3A) or Formula (3B) is more preferable.
##STR00018##
[0220] X.sup.3, Y.sup.3, Z.sup.3, and p in Formula (3A) or Formula
(3B) are the same as X.sup.3, Y.sup.3, Z.sup.3, and p in Formula
(3) described above.
[0221] It is more preferable that the polymer compound contains, as
a structural unit containing a graft chain, particularly, a polymer
chain, a structural unit represented by Formula (1A).
[0222] The content of the structural unit containing a graft chain
(for example, the structural unit represented by any of Formula (1)
to Formula (4)) in the polymer compound that is expressed in terms
of mass is preferably 2% to 90% by mass and more preferably within
a range of 5% to 30% by mass with respect to the total mass of the
polymer compound. In a case where the content of the structural
unit containing a graft chain in the polymer compound is within the
above range, the dispersant more easily disperses the pigment and
the like, and the curable composition has better
developability.
[0223] Hydrophobic Structural Unit
[0224] It is preferable that the polymer compound contains a
hydrophobic structural unit different from the structural unit
containing a graft chain (that is, a hydrophobic structural unit
which does not correspond to the structural unit containing a graft
chain). Here, in the present specification, the hydrophobic
structural unit is a structural unit which does not contain an acid
group (for example, a carboxylic acid group, a sulfonic acid group,
a phosphoric acid group, a phenolic hydroxyl group, or the
like).
[0225] As the hydrophobic structural unit, a structural unit
derived from (corresponding to) a compound (monomer) having a ClogP
value, which will be described later, equal to or greater than 1.2
is preferable, and a structural unit derived from a compound having
a ClogP value of 1.2 to 8.0 is more preferable.
[0226] The ClogP value is a value calculated by a program "CLOGP"
available from Daylight Chemical Information System, Inc. This
program provides a value of "calculated logP" calculated by the
fragment approach (see the following documents) of Hansch and Leo.
The fragment approach is based on the chemical structure of a
compound. In this method, the chemical structure is divided into
partial structures (fragments), and degrees of contribution to logP
that are assigned to the fragments are summed up, thereby
estimating the logP value of the compound. Details of the method
are described in the following documents. In the present invention,
a ClogP value calculated by a program CLOGP v 4.82 is used.
[0227] A. J. Leo, Comprehensive Medicinal Chemistry, Vol. 4, C.
Hansch, P. G. Sammnens
[0228] J. B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon
press, 1990
[0229] C. Hansch & A. J. Leo. Substituent Constants For
Correlation Analysis in Chemistry and Biology. John Wiley &
Sons.
[0230] A. J. Leo. Calculating logPoct from structure. Chem. Rev.,
93, 1281-1306, 1993.
[0231] logP means a common logarithm of a partition coefficient P.
logP is a value of physical properties that shows how a certain
organic compound is partitioned in an equilibrium of two-phase
system consisting of oil (generally, 1-octanol) and water by using
a quantitative numerical value. logP is represented by the
following formula.
log P=log(Coil/Cwater)
[0232] In the formula, Coil represents a molar concentration of a
compound in an oil phase, and Cwater represents a molar
concentration of the compound in a water phase.
[0233] The greater the positive logP value based on 0, the higher
the oil solubility. The greater the absolute value of negative
logP, the higher the water solubility. The value of logP is
negatively correlated with the water solubility of an organic
compound, and widely used as a parameter for estimating the
hydrophilicity and hydrophobicity of an organic compound.
[0234] It is preferable that the polymer compound contains, as a
hydrophobic structural unit, at least one kind of structural unit
selected from the group consisting of structural units derived from
monomers represented by Formulae (i) to (iii).
##STR00019##
[0235] In Formulae (i) to (iii), R.sup.1, R.sup.2, and R.sup.3 each
independently represent a hydrogen atom, a halogen atom (for
example, a fluorine atom, a chlorine atom, a bromine atom, or the
like), or an alkyl group having 1 to 6 carbon atoms (for example, a
methyl group, an ethyl group, a propyl group, or the like).
[0236] As each of R.sup.1, R.sup.2, and R.sup.3, a hydrogen atom or
an alkyl group having 1 to 3 carbon atoms is preferable, and a
hydrogen atom or a methyl group is more preferable. As each of
R.sup.2 and R.sup.3, a hydrogen atom is even more preferable.
[0237] X represents an oxygen atom (--O--) or an imino group
(--NH--). X is preferably an oxygen atom.
[0238] L represents a single bond or a divalent linking group.
Examples of the divalent linking group include a divalent aliphatic
group (for example, an alkylene group, a substituted alkylene
group, an alkenylene group, a substituted alkenylene group, an
alkynylene group, a substituted alkynylene group, or the like), a
divalent aromatic group (for example, an arylene group, a
substituted arylene group, or the like), a divalent heterocyclic
group, an oxygen atom (--O--), a sulfur atom (--S--), an imino
group (--NH--), a substituted imino group (--NR.sup.31--, R.sup.31
represents an aliphatic group, an aromatic group, or a heterocyclic
group), a carbonyl group (--CO--), a combination of these, and the
like.
[0239] The divalent aliphatic group may contain a cyclic structure
or a branched structure. The number of carbon atoms in the
aliphatic group is preferably 1 to 20, more preferably 1 to 15, and
even more preferably 1 to 10. The aliphatic group may be an
unsaturated aliphatic group or a saturated aliphatic group. As the
aliphatic group, a saturated aliphatic group is preferable.
Furthermore, the aliphatic group may have a substituent. The
substituent is not particularly limited, and examples thereof
include a halogen atom, an aromatic group, a heterocyclic group,
and the like.
[0240] The number of carbon atoms in the divalent aromatic group is
preferably 6 to 20, more preferably 6 to 15, and even more
preferably 6 to 10. Furthermore, the aromatic group may have a
substituent. The substituent is not particularly limited, and
examples thereof include a halogen atom, an aliphatic group, an
aromatic group, a heterocyclic group, and the like.
[0241] It is preferable that the divalent heterocyclic group
contain, as a heterocyclic ring, a 5-membered ring or a 6-membered
ring. The heterocyclic ring may be fused with another heterocyclic
ring, aliphatic ring, or aromatic ring. Furthermore, the
heterocyclic group may have a substituent. The substituent is not
particularly limited, and examples thereof include a halogen atom,
a hydroxyl group, an oxo group (.dbd.O), a thioxo group (.dbd.S),
an imino group (.dbd.NH), a substituted imino group
(.dbd.N--R.sup.32, R.sup.32 is an aliphatic group, an aromatic
group, or a heterocyclic group), an aliphatic group, an aromatic
group, a heterocyclic group, and the like.
[0242] As L, a single bond, an alkylene group, or a divalent
linking group containing an oxyalkylene structure is preferable.
The oxyalkylene structure is more preferably an oxyethylene
structure or an oxypropylene structure. Furthermore, L may contain
a polyoxyalkylene structure which contains two or more repeating
oxyalkylene structures. As the polyoxyalkylene structure, a
polyoxyethylene structure or a polyoxypropylene structure is
preferable. The polyoxyethylene structure is represented by
--(OCH.sub.2CH.sub.2)n-, and n is preferably an integer equal to or
greater than 2 and more preferably an integer of 2 to 10.
[0243] Examples of Z include an aliphatic group (for example, an
alkyl group, a substituted alkyl group, an unsaturated alkyl group,
a substituted unsaturated alkyl group, or the like), an aromatic
group (for example, an aryl group, a substituted aryl group, an
arylene group, a substituted arylene group, or the like), a
heterocyclic group, and a combination of these. These groups may
contain an oxygen atom (--O--), a sulfur atom (--S--), an imino
group (--NH--), a substituted imino group (--NR.sup.31--, R.sup.31
represents an aliphatic group, an aromatic group, or a heterocyclic
group), or a carbonyl group (--CO--).
[0244] The aliphatic group may contain a cyclic structure or a
branched structure. The number of carbon atoms in the aliphatic
group is preferably 1 to 20, more preferably 1 to 15, and even more
preferably 1 to 10. The aliphatic group further contains a
ring-aggregated hydrocarbon group or a crosslinked ring-type
hydrocarbon group. Examples of the ring-aggregated hydrocarbon
group include a bicyclohexyl group, a perhydronaphthalenyl group, a
biphenyl group, a 4-cyclohexylphenyl group, and the like. Examples
of the crosslinked ring-type hydrocarbon ring include a bicyclic
hydrocarbon ring such as a pinane, bornane, norpinane, norbornane,
or bicyclooctane ring (a bicyclo[2.2.2]octane ring, a
bicyclo[3.2.1]octane ring, or the like); a tricyclic hydrocarbon
ring such as adamantane, tricyclo[5.2.1.0.sup.2,6]decane, or
tricyclo[4.3.1.1.sup.2,5]undecane ring; a tetracyclic hydrocarbon
ring such as tetracyclo[4.4.0.1.sup.2,5.1.sup.7,10]dodecane or
perhydro-1,4-methano-5,8-methanonaphthalene ring; and the like. The
crosslinked ring-type hydrocarbon ring also includes a fused
ring-type hydrocarbon ring, for example, a fused ring in which a
plurality of 5- to 8-membered cycloalkane rings such as
perhydronaphthalene (decalin), perhydroanthracene,
perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene,
perhydroindene, and perhydrophenalene rings are fused.
[0245] As the aliphatic group, a saturated aliphatic group is more
preferable than an unsaturated aliphatic group. Furthermore, the
aliphatic group may have a substituent. Examples of the substituent
include a halogen atom, an aromatic group, a heterocyclic group,
and the like. Here, the aliphatic group does not contain an acid
group as a substituent.
[0246] The number of carbon atoms in the aromatic group is
preferably 6 to 20, more preferably 6 to 15, and even more
preferably 6 to 10. Furthermore, the aromatic group may have a
substituent. Examples of the substituent include a halogen atom, an
aliphatic group, an aromatic group, a heterocyclic group, and the
like. Here, the aromatic group does not contain an acid group as a
substituent.
[0247] It is preferable that the heterocyclic group contains a
5-membered ring or a 6-membered ring as a heterocyclic ring.
Another heterocyclic ring, aliphatic ring, or aromatic ring may be
fused with the heterocyclic ring. Furthermore, the heterocyclic
group may have a substituent. Examples of the substituent include a
halogen atom, a hydroxyl group, an oxo group (.dbd.O), a thioxo
group (.dbd.S), an imino group (.dbd.NH), a substituted imino group
(.dbd.N--R.sup.32, R.sup.32 is an aliphatic group, an aromatic
group, or a heterocyclic group), an aliphatic group, an aromatic
group, a heterocyclic group, and the like. Here, the heterocyclic
group does not have an acid group as a substituent.
[0248] In Formula (iii), R.sup.4, R.sup.5, and R.sup.6 each
independently represent a hydrogen atom, a halogen atom (for
example, a fluorine atom, a chlorine atom, a bromine atom, or the
like), an alkyl group having 1 to 6 carbon atoms (for example, a
methyl group, an ethyl group, a propyl group, or the like), Z, or
L-Z. L and Z have the same definition as L and Z described above.
As R.sup.4, R.sup.5, and R.sup.6, a hydrogen atom or an alkyl group
having 1 to 3 carbon atoms is preferable, and a hydrogen atom is
more preferable.
[0249] As the monomer represented by Formula (i), a compound is
preferable in which R.sup.1, R.sup.2, and R.sup.3 each represent a
hydrogen atom or a methyl group, L represents a single bond, an
alkylene group, or a divalent linking group containing an
oxyalkylene structure, X represents an oxygen atom or an imino
group, and Z represents an aliphatic group, a heterocyclic group,
or an aromatic group.
[0250] As the monomer represented by Formula (ii), a compound is
preferable in which R.sup.1 represents a hydrogen atom or a methyl
group, L represents an alkylene group, and Z represents an
aliphatic group, a heterocyclic group, or an aromatic group. As the
monomer represented by Formula (iii), a compound is preferable in
which R.sup.4, R.sup.5, and R.sup.6 each represent a hydrogen atom
or a methyl group, and Z represents an aliphatic group, a
heterocyclic group, or an aromatic group.
[0251] Examples of typical compounds represented by Formulae (i) to
(iii) include radically polymerizable compounds such as acrylic
acid esters, methacrylic acid esters, and styrenes.
[0252] Regarding typical compounds represented by Formula (i) to
(iii), the compounds described in paragraphs "0089" to "0093" in
JP2013-249417A can be referred to, and the contents of the
paragraphs are incorporated into the present specification.
[0253] The content of the hydrophobic structural unit with respect
to the total mass of the polymer compound is preferably 10% to 90%
by mass, and more preferably 20% to 80% by mass. In a case where
the content of the hydrophobic structural unit is within the above
range, the curable composition has a better pattern forming
performance.
[0254] Structural Unit Containing Functional Group Capable of
Interacting with Pigment and the Like.
[0255] A functional group capable of interacting with the pigment
and the like can be introduced into the polymer compound. It is
preferable that the polymer compound further contains a structural
unit which contains a functional group capable of interacting with
the pigment and the like.
[0256] Examples of the functional group capable of interacting with
the pigment and the like include an acid group, a basic group, a
coordinating group, a reactive functional group, and the like.
[0257] In a case where the polymer compound contains an acid group,
a basic group, a coordinating group, or a reactive functional
group, it is preferable that the polymer compound contains each of
a structural unit containing an acid group, a structural unit
containing a basic group, a structural unit containing a
coordinating group, or a reactive structural unit.
[0258] Particularly, in a case where the polymer compound further
contains, as an acid group, an alkali-soluble group such as a
carboxylic acid group, developability for forming a pattern by
alkali development can be imparted to the polymer compound.
[0259] That is, in a case where an alkali-soluble group is
introduced into the polymer compound, in the curable composition,
the polymer compound as a dispersant making a contribution to the
dispersion of the pigment and the like also has alkali solubility.
The curable composition containing such a polymer compound has
better alkali developability (an unexposed portion is more easily
dissolved by alkali development), and the obtained cured film has
better light blocking properties.
[0260] The polymer compound containing an acid group exhibits
higher affinity with the solvent which will be described later.
Accordingly, the curable composition which contains the polymer
compound containing an acid group has better coating
properties.
[0261] Presumably, this is because the acid group in the structural
unit containing an acid group may easily interact with the pigment
and the like, the polymer compound may stably disperse the pigment
and the like, the viscosity of the polymer compound dispersing the
pigment and the like may be reduced, and hence the polymer compound
may also be easily dispersed in a stable manner.
[0262] The structural unit containing an alkali-soluble group as an
acid group may be the same as or different from the structural unit
containing a graft chain described above.
[0263] In the present specification, the structural unit containing
an alkali-soluble group as an acid group means a structural unit
different from the hydrophobic structural unit described above
(that is, the structural unit does not correspond to the
hydrophobic structural unit).
[0264] Among functional groups capable of interacting with the
pigment and the like, examples of acid groups include a carboxylic
acid group, a sulfonic acid group, a phosphoric acid group, a
phenolic hydroxyl group, and the like. Among these, at least one
kind of acid group selected from the group consisting of a
carboxylic acid group, a sulfonic acid group, and a phosphoric acid
group is preferable, and a carboxylic acid group is more preferable
because this group exhibits higher adsorptivity with respect to the
pigment and the like and has better dispersibility.
[0265] That is, it is preferable that the polymer compound further
contains a structural unit which contains at least one kind of acid
group selected from the group consisting of a carboxylic acid
group, a sulfonic acid group, and a phosphoric acid group.
[0266] The polymer compound may have one kind of structural unit
containing an acid group or two or more kinds of structural units
containing an acid group.
[0267] The polymer compound may or may not contain the structural
unit containing an acid group.
[0268] In the polymer compound, the content of the structural unit
containing an acid group with respect to the total mass of the
polymer compound is preferably 5% to 80% by mass, and more
preferably 10% to 60% by mass in view of further inhibiting the
image intensity from being damaged by alkali development.
[0269] Among the functional groups capable of interacting with the
pigment and the like, examples of basic groups include a primary
amino group, a secondary amino group, a tertiary amino group, a
hetero ring containing a N atom, an amide group, and the like.
Among these, a tertiary amino group is preferable because this
exhibits higher adsorptivity with respect to the pigment and the
like and has better dispersibility. The polymer compound may
contain one kind of basic group or two or more kinds of basic
groups. The polymer compound may or may not contain the structural
unit containing a basic group.
[0270] In the polymer compound, the content of the structural unit
containing a basic group with respect to the total mass of the
polymer compound is preferably 0.01% to 50% by mass, and more
preferably 0.01% to 30% by mass because that the curable
composition has better developability (because then it is more
difficult for the alkali development to be hindered).
[0271] Among the functional groups capable of interacting with the
pigment and the like, examples of coordinating groups and reactive
functional groups include an acetyl acetoxy group, a trialkoxysilyl
group, an isocyanate group, an acid anhydride, an acid chloride,
and the like. Among these, acetyl acetoxy group is preferable
because this exhibits higher adsorptivity with respect to the
pigment and the like and more easily disperses the pigment and the
like. The polymer compound may contain one kind of coordinating
group and one kind of reactive functional group, or contain two or
more kinds of coordinating groups and reactive functional groups.
The polymer compound may or may not contain both the structural
unit containing a coordinating group and the structural unit
containing a reactive functional group.
[0272] In the polymer compound, the content of the structural unit
containing a coordinating group and the reactive functional group
with respect to the total mass of the polymer compound is
preferably 10% to 80% by mass, and more preferably 20% to 60% by
mass because that the curable composition has better developability
(because then it is more difficult for the alkali development to be
hindered).
[0273] In a case where the polymer compound contains the functional
group capable of interacting with the pigment and the like in
addition to the graft chain, the polymer compound just need to
contain the functional group capable of interacting with the
pigment and the like, and the way the functional group is
introduced into the polymer compound is not particularly limited.
It is preferable that the polymer compound contains one or more
kind of structural units selected from structural units derived
from monomers represented by Formulae (iv) to (vi).
##STR00020##
[0274] In Formula (iv) to Formula (vi), R.sup.11, R.sup.12, and
R.sup.13 each independently represent a hydrogen atom, a halogen
atom (for example, a fluorine atom, a chlorine atom, a bromine
atom, or the like), or an alkyl group having 1 to 6 carbon atoms
(for example, a methyl group, an ethyl group, a propyl group, or
the like).
[0275] In Formula (iv) to Formula (vi), R.sup.11, R.sup.12, and
R.sup.13 preferably each independently represent a hydrogen atom or
an alkyl group having 1 to 3 carbon atoms, and more preferably each
independently represent a hydrogen atom or a methyl group. In
Formula (iv), R.sup.12 and R.sup.13 are even more preferably each
represent a hydrogen atom.
[0276] In Formula (iv), X.sub.1 represents an oxygen atom (--O--)
or an imino group (--NH--), and preferably represents an oxygen
atom.
[0277] In Formula (v), Y represents a methine group or a nitrogen
atom.
[0278] In Formula (iv) to Formula (v), L.sub.1 represents a single
bond or a divalent linking group. The divalent linking group has
the same definition as the divalent linking group represented by L
in Formula (i) described above.
[0279] As L.sub.1, a single bond, an alkylene group, or a divalent
linking group containing an oxyalkylene structure is preferable. As
the oxyalkylene structure, an oxyethylene structure or an
oxypropylene structure is more preferable. Furthermore, L.sub.1 may
contain a polyoxyalkylene structure containing two or more
repeating oxyalkylene structures. As the polyoxyalkylene structure,
a polyoxyethylene structure or a polyoxypropylene structure is
preferable. The polyoxyethylene structure is represented by
--(OCH.sub.2CH.sub.2)n-, and n is preferably an integer equal to or
greater than 2 and more preferably an integer of 2 to 10.
[0280] In Formula (iv) to Formula (vi), Z.sub.1 represents a
functional group capable of interacting with the pigment and the
like other than a graft chain. As Z.sub.1, a carboxylic acid group
and a tertiary amino group are preferable, and a carboxylic acid
group is more preferable.
[0281] In Formula (vi), R.sup.14, R.sup.15, and R.sup.16 each
independently represent a hydrogen atom, a halogen atom (for
example, a fluorine atom, a chlorine atom, a bromine atom, or the
like), an alkyl group having 1 to 6 carbon atoms (for example, a
methyl group, an ethyl group, a propyl group, or the like),
--Z.sub.1, or L.sub.1-Z.sub.1. L.sub.1 and Z.sub.1 have the same
definition as L.sub.1 and Z.sub.1 described above, and preferred
examples thereof are also the same. R.sup.14, R.sup.15, and
R.sup.16 preferably each independently represent a hydrogen atom or
an alkyl group having 1 to 3 carbon atoms, and more preferably each
independently represent a hydrogen atom.
[0282] As the monomer represented by Formula (iv), a compound is
preferable in which R.sup.11, R.sup.12, and R.sup.13 each
independently represent a hydrogen atom or a methyl group, L.sub.1
represents an alkylene group or a divalent linking group containing
an oxyalkylene structure, X.sub.1 represents an oxygen atom or an
imino group, and Z.sub.1 represents a carboxylic acid group.
[0283] As the monomer represented by Formula (v), a compound is
preferable in which R.sup.11 represents a hydrogen atom or a methyl
group, L.sub.1 represents an alkylene group, Z.sub.1 represents a
carboxylic acid group, and Y represents a methine group.
[0284] As the monomer represented by Formula (vi), a compound is
preferable in which R.sup.14, R.sup.15, and R.sup.16 each
independently represent a hydrogen atom or a methyl group, L.sub.1
represents a single bond or an alkylene group, and Z.sub.1
represents a carboxylic acid group.
[0285] Typical examples of the monomers (compounds) represented by
Formula (iv) to Formula (vi) are as below.
[0286] Examples of the monomers include methacrylic acid, crotonic
acid, isocrotonic acid, a product of a reaction between a compound
containing an addition polymerizable double bond and a hydroxyl
group in a molecule (for example, 2-hydroxyethyl methacrylate) and
succinic acid anhydride, a product of a reaction between a compound
containing an addition polymerizable double bond and a hydroxyl
group in a molecule and phthalic acid anhydride, a product of a
reaction between a compound containing an addition polymerizable
double bond and a hydroxyl group in a molecule and
tetrahydrophthalic acid anhydride, a product of a reaction between
a compound containing an addition polymerizable double bond and a
hydroxyl group in a molecule and trimellitic acid anhydride, a
product of a reaction between a compound containing an addition
polymerizable double bond and a hydroxyl group in a molecule and
pyromellitic acid anhydride, acrylic acid, an acrylic acid dimer,
an acrylic acid oligomer, maleic acid, itaconic acid, fumaric acid,
4-vinylbenzoic acid, vinyl phenol, 4-hydroxyphenyl methacrylamide,
and the like.
[0287] In the polymer compound, from the viewpoint of the
interaction with the pigment and the like, the temporal stability,
and the permeability with respect to a developer, the content of
the structural unit containing a functional group capable of
interacting with the pigment and the like with respect to the total
mass of the polymer compound is preferably 0.05% to 90% by mass,
more preferably 1.0% to 80% by mass, and even more preferably 10%
to 70% by mass.
[0288] Other Structural Units
[0289] For the purpose of improving various performances such as
image intensity, as long as the effects of the present invention
are not impaired, the polymer compound may further contain other
structural units (for example, a structural unit containing a
functional group or the like having affinity with the solvent used
in a dispersed composition, and the like) that are different from
the structural unit containing a graft chain, the hydrophobic
structural unit, and the structural unit containing a functional
group capable of interacting with the pigment and the like.
[0290] Examples of those other structural units include structural
units derived from radically polymerizable compounds selected from
the group consisting of acrylonitriles and methacrylonitriles, and
the like.
[0291] The polymer compound may contain one kind of those other
structural units or two or more kinds of those other structural
units.
[0292] In the polymer compound, the content of those other
structural units with respect to the total mass of the polymer
compound is preferably 0% to 80% by mass, and more preferably 10%
to 60% by mass. In a case where the content of those other
structural units is 0% to 80% by mass, the curable composition has
better pattern forming properties.
[0293] Physical Properties of Polymer Compound
[0294] The acid value of the polymer compound is not particularly
limited, but is preferably 0 to 250 mgKOH/g, more preferably 10 to
200 mgKOH/g, and even more preferably 20 to 120 mgKOH/g.
[0295] In a case where the acid value of the polymer compound is
equal to or lower than 250 mgKOH/g, the peeling of the cured film
from a substrate that occurs in the development step, which will be
described later, is further inhibited. In a case where the acid
value of the polymer compound is equal to or higher than 10
mgKOH/g, the curable composition has better alkali
developability.
[0296] In a case where the acid value of the polymer compound is
equal to or higher than 20 mgKOH/g, the precipitation of the
pigment and the like in the curable composition is further
inhibited, and the number of coarse particles is further reduced.
Consequently, the curable composition has better temporal
stability.
[0297] The acid value of the polymer compound can be calculated,
for example, from the average content of acid groups in the polymer
compound. Furthermore, by changing the content of the acid
group-containing structural unit in the polymer compound, a polymer
compound having the desired acid value can be obtained.
[0298] In order for the curable composition to have better
developability and in order to make it more difficult for the
obtained cured film to be peeled in the development step, the
weight-average molecular weight of the polymer compound that is
determined by Gel Permeation Chromatography (GPC) and expressed in
terms of polystyrene is preferably 4,000 to 300,000, more
preferably 5,000 to 200,000, even more preferably 6,000 to 100,000,
and particularly preferably 10,000 to 50,000.
[0299] GPC is based on a method of using HLC-8020GPC (manufactured
by Tosoh Corporation), TSKgel SuperHZM-H, TSKgel SuperHZ4000, and
TSKgel SuperHZ2000 (manufactured by Tosoh Corporation, 4.6
mmID.times.15 cm) as columns, and tetrahydrofuran (THF) as an
eluent. The polymer compound can be synthesized based on known
methods.
[0300] Specific examples of the polymer compound include "DA-7301"
manufactured by Kusumoto Chemicals. Ltd., "Disperbyk-101
(polyamidoamine phosphate), 107 (carboxylic acid ester), 110
(copolymer containing an acid group), 111 (phosphoric acid-based
dispersant), 130 (polyamide), 161, 162, 163, 164, 165, 166, 170,
and 190 (polymeric copolymer)" and "BYK-P104 and P105
(high-molecular-weight unsaturated polycarboxylic acid)"
manufactured by BYKChemie GmbH, "EFKA 4047, 4050 to 4010 to 4165
(based on polyurethane), EFKA 4330 to 4340 (block copolymer), 4400
to 4402 (modified polyacrylate), 5010 (polyester amide), 5765
(high-molecular-weight carboxylate), 6220 (aliphatic polyester),
6745 (phthalocyanine derivative), and 6750 (azo pigment derivative"
manufactured by EFKA, "AJISPER PB821, PB822, PB880, and PB881"
manufactured by Ajinomoto Fine-Techno Co., Inc., "FLOWLEN TG-710
(urethane oligomer)" and "POLYFLOW No. 50E, No. 300 (acrylic
copolymer)" manufactured by KYOEISHA CHEMICAL Co., LTD, "DISPARLON
KS-860, 873SN, 874, #2150 (aliphatic polyvalent carboxylic acid),
#7004 (polyether ester), DA-703-50, DA-705, and DA-725"
manufactured by Kusumoto Chemicals. Ltd., "DEMOL RN, N
(naphthalenesulfonic acid formalin polycondensate), MS, C, and SN-B
(aromatic sulfonic acid formalin polycondensate)", "HOMOGENOL L-18
(polymeric polycarboxylic acid)", "EMULGEN 920, 930, 935, and 985
(polyoxyethylene nonylphenyl ether)", and "ACETAMIN 86
(stearylamine acetate)" manufactured by Kao Corporation, "SOLSPERSE
5000 (phthalocyanine derivative), 22000 (azo pigment derivative),
13240 (polyester amine), 3000, 12000, 17000, 20000, 27000 (polymer
containing a functional portion on a terminal portion), 24000,
28000, 32000, and 38500 (graft copolymer)" manufactured by Lubrizol
Japan Limited, "NIKKOL T106 (polyoxyethylene sorbitan monooleate),
and MYS-IEX (polyoxyethylene monostearate)" manufactured by Nikko
Chemicals Co., Ltd., HINOACT T-8000E and the like manufactured by
Kawaken Fine Chemicals Co., Ltd., an organosiloxane polymer KP-341
manufactured by Shin-Etsu Chemical Co., Ltd., "W001: cationic
surfactant" manufactured by Yusho Co., Ltd., nonionic surfactants
such as polyoxyethylene lauryl ether, polyoxyethylene stearyl
ether, polyoxyethylene oleyl ether, polyoxyethylene octyl phenyl
ether, polyoxyethylene nonyl phenyl ether, polyethylene glycol
dilaurate, polyethylene glycol distearate, and a sorbitan fatty
acid ester, anionic surfactants such as "W004, W005, and W017",
polymer dispersants such as "EFKA-46, EFKA-47, EFKA-47EA, EFKA
polymer 100, EFKA polymer 400, EFKA polymer 401, and EFKA polymer
450" manufactured by MORISHITA & CO., LTD., and "DISPERSE AID
6, DISPERSE AID 8, DISPERSE AID 15, and DISPERSE AID 9100"
manufactured by SAN NOPCO LIMITED, "ADEKA PLURONIC L31, F38, L42,
L44, L61, L64, F68, L72, P95, F77, P84, F87, P94, L101, P103, F108,
L121, and P-123" manufactured by ADEKA CORPORATION, "IONET (trade
name) S-20" manufactured by Sanyo Chemical Industries, Ltd., and
the like. Furthermore, ACRYBASE FFS-6752, ACRYBASE FFS-187,
ACRYCURE RD-F8, and CYCLOMER P can also be used.
[0301] Furthermore, it is also possible to use DISPERBYK-130,
DISPERBYK-140, DISPERBYK-142, DISPERBYK-145, DISPERBYK-180,
DISPERBYK-187, DISPERBYK-191, DISPERBYK-2001, DISPERBYK-2010,
DISPERBYK-2012, DISPERBYK-2025, and BYK-9076 manufactured by
BYKChemie GmbH, AJISPER PB821, AJISPER PB822, and AJISPER PB881
manufactured by Ajinomoto Fine-Techno Co., Inc., and the like.
[0302] One kind of these polymer compounds may be used singly, or
two or more kinds of these polymer compounds may be used in
combination.
[0303] As the polymer compound, the compounds described in
paragraphs "0127" to "0129" in JP2013-249417A can also be used, and
the contents of the paragraphs are incorporated into the present
specification.
[0304] Furthermore, as a dispersant, it is also possible to use the
graft copolymers described in paragraphs "0037" to "0115" in
JP2010-106268A (paragraphs "0075" to "0133" in US2011/0124824A
corresponding to JP2010-106268A), and the contents of the
paragraphs are incorporated into the present specification.
[0305] In addition, as a dispersant, it is also possible to use the
polymer compounds described in paragraphs "0028" to "0084" in
JP2011-153283A (paragraphs "0075" to "0133" in US2011/0279759A
corresponding to JP2011-153283A) that contain a constituent
component containing a side chain structure formed by bonding of
acidic groups through a linking group, and the contents of the
paragraphs are incorporated into the present specification.
[0306] Moreover, as a dispersant, the resins described in
paragraphs "0033" to "0049" in JP2016-109763A can also be used, and
the contents of the paragraphs are incorporated into the present
specification.
[0307] (E2: Alkali-Soluble Resin)
[0308] It is preferable that the curable composition contains an
alkali-soluble resin (corresponding to a resin). In the present
specification, the alkali-soluble resin means a resin which
contains a group promoting alkali solubility (alkali-soluble group)
and is different from the dispersant described above.
[0309] The content of the alkali-soluble resin in the curable
composition is not particularly limited. In order for the curable
composition to have better patterning properties, the content of
the alkali-soluble resin with respect to the total solid content of
the curable composition is preferably equal to or greater than 0.1%
by mass, more preferably equal to or greater than 0.5% by mass,
even more preferably equal to or greater than 2.0% by mass, and
particularly preferably equal to or greater than 7.3% by mass. The
upper limit of the content of the alkali-soluble resin is not
particularly limited, but is preferably equal to or smaller than
30% by mass in general.
[0310] One kind of alkali-soluble resin may be used singly, or two
or more kinds of alkali-soluble resins may be used in combination.
In a case where two or more kinds of alkali-soluble resins are used
in combination, the total content thereof is preferably within the
above range.
[0311] Examples of the alkali-soluble resin include a resin
containing at least one alkali-soluble group in a molecule.
Examples thereof include a polyhydroxystyrene resin, a polysiloxane
resin, a (meth)acryl resin, a (meth)acrylamide resin, a
(meth)acryl/(meth)acrylamide copolymer resin, an epoxy-based resin,
a polyimide resin, and the like.
[0312] Specific examples of the alkali-soluble resin include a
copolymer of an unsaturated carboxylic acid and an ethylenically
unsaturated compound.
[0313] The unsaturated carboxylic acid is not particularly limited,
and examples thereof include monocarboxylic acids such as
(meth)acrylic acid, crotonic acid, and vinyl acetate; dicarboxylic
acid such as itaconic acid, maleic acid, or fumaric acid or an acid
anhydride of these; polyvalent carboxylic acid monoesters such as
mono(2-(meth)acryloyloxyethyl)phthalate; and the like.
[0314] Examples of copolymerizable ethylenically unsaturated
compounds include methyl (meth)acrylate and the like. Furthermore,
it is also possible to use the compounds described in paragraph
"0027" in JP2010-097210A and paragraphs "0036" and "0037" in
JP2015-068893A, and the contents of the paragraphs are incorporated
into the present specification.
[0315] Furthermore, copolymerizable ethylenically unsaturated
compounds containing an ethylenically unsaturated group on a side
chain may also be used in combination. As the ethylenically
unsaturated group, a (meth)acrylic acid group is preferable. An
acrylic resin containing an ethylenically unsaturated group on a
side chain can be obtained, for example, by addition-reacting a
carboxylic acid group of an acrylic resin containing a carboxylic
acid group with an ethylenically unsaturated compound containing a
glycidyl group or an alicyclic epoxy group.
[0316] As the alkali-soluble resin, for example, it is possible to
use the radical polymer containing a carboxylic acid group on a
side chain described in JP1984-044615A (JP-S59-044615A),
JP1979-034327B (JP-S54-034327B), JP1983-012577B (JP-S58-012577B),
JP1979-025957B (JP-S54-025957B), JP1979-092723A (JP-S54-092723A),
JP1984-053836A (JP-S59-053836A), and JP1984-071048A
(JP-S59-071048A); the acetal-modified polyvinyl alcohol-based
binder resin containing an alkali-soluble group described in
EP993966B, EP1204000B, and JP2001-318463A; polyvinyl pyrrolidone;
polyethylene oxide; polyether as a product of a reaction between
alcohol-soluble nylon, 2,2-bis-(4-hydroxyphenyl)-propane, and
epichlorohydrin; the polyimide resin described in WO2008/123097A;
and the like.
[0317] As the alkali-soluble resin, the compounds described in
paragraphs "0225" to "0245" in JP2016-075845A can also be used, and
the contents of the paragraphs are incorporated into the present
specification.
[0318] As the alkali-soluble resin, a polyimide precursor can also
be used. The polyimide precursor means a resin obtained by causing
an addition polymerization reaction between a compound containing
an acid anhydride group and a diamine compound at a temperature of
40.degree. C. to 100.degree. C.
[0319] Examples of the polyimide precursor include a resin
containing a repeating unit represented by Formula (1). For
example, the polyimide precursor has an amic acid structure
represented by Formula (2) and an imide structure represented by
Formula (3) obtained in a case where imide ring opening occurs in a
portion of an amic acid structure and/or represented by Formula (4)
obtained in a case where imide ring opening occurs in the entirety
of an amic acid structure.
[0320] In the present specification, the polyimide precursor having
an amic acid structure is referred to as polyamic acid in some
cases.
##STR00021##
[0321] In Formulae (1) to (4), R.sub.1 represents a quadrivalent
organic group having 2 to 22 carbon atoms, R.sub.2 represents a
divalent organic group having 1 to 22 carbon atoms, and n
represents 1 or 2.
[0322] Examples of the polyimide precursor include the compounds
described in paragraphs "0011" to "0031" in JP2008-106250A, the
compounds described in paragraphs "0022" to "0039" in
JP2016-122101A, the compounds described in paragraphs "0061" to
"0092" in JP2016-068401A, and the like. The contents of the
paragraphs are incorporated into the present specification.
[0323] In view of the better pattern shape of the cured film
obtained from the curable composition, it is preferable that the
alkali-soluble resin contains at least one kind of component
selected from the group consisting of a polyimide resin and a
polyimide precursor.
[0324] As the polyimide resin containing the alkali-soluble resin,
known polyimide resins containing the alkali-soluble group can be
used without particular limitation. Examples of the polyimide resin
include the resin described in paragraph "0050" in JP2014-137523A,
the resin described in paragraph "0058" in JP2015-187676A, the
resin described in paragraphs "0012" and "0013" in JP2014-106326A,
and the like. The contents of the paragraphs are incorporated into
the present specification.
[0325] <F: Surfactant>
[0326] It is preferable that the curable composition contains a
surfactant. The curable composition containing a surfactant has
better coating properties.
[0327] The content of the surfactant in the curable composition is
not particularly limited. The content of the surfactant with
respect to the total solid content of the curable composition is
preferably 0.001% to 2.0% by mass.
[0328] One kind of surfactant may be used singly, or two or more
kinds of surfactants may be used in combination. In a case where
two or more kinds of surfactants are used in combination, the total
content thereof is preferably within the above range.
[0329] Examples of the surfactant include a fluorine-based
surfactant, a nonionic surfactant, a cationic surfactant, an
anionic surfactant, a silicone-based surfactant, and the like.
[0330] For example, in a case where the curable composition
contains a fluorine-based surfactant, the liquid characteristics
(particularly, fluidity) of the curable composition are further
improved. That is, in a case where a curable composition layer is
formed on a substrate by using the curable composition containing
the fluorine-based surfactant, the interfacial tension between the
substrate and the curable composition is reduced, and accordingly,
the wettability with respect to the substrate is improved, and the
coating properties of the curable composition are improved.
Therefore, even in a case where a curable composition layer having
a thickness of about several micrometers is formed of a small
amount of the curable composition, a curable composition layer
having a more uniform thickness and small thickness unevenness can
be formed.
[0331] The content of fluorine in the fluorine-based surfactant is
not particularly limited, but is preferably 3% to 40% by mass, more
preferably 5% to 30% by mass, and even more preferably 7% to 25% by
mass. In a case where a curable composition, which contains a
fluorine-based surfactant with a fluorine content of 3% to 40% by
mass, is used, a curable composition layer having a more uniform
thickness can be formed. As a result, the curable composition has
better liquid saving properties. Furthermore, in a case where the
fluorine content is within the above range, the fluorine-based
surfactant is more easily dissolved in the curable composition.
[0332] Examples of the fluorine-based surfactant include MEGAFACE
F171, MEGAFACE F172, MEGAFACE F173, MEGAFACE F176, MEGAFACE F177,
MEGAFACE F141, MEGAFACE F142, MEGAFACE F143, MEGAFACE F144,
MEGAFACE R30, MEGAFACE F437, MEGAFACE F475, MEGAFACE F479, MEGAFACE
F482, MEGAFACE F554, and MEGAFACE F780 (manufactured by DIC
Corporation), FLUORAD FC430, FLUORAD FC431, and FLUORAD FC171
(manufactured by Sumitomo 3M Limited), SURFLON S-382, SURFLON
SC-101, SURFLON SC-103, SURFLON SC-104, SURFLON SC-105, SURFLON
SC-1068, SURFLON SC-381, SURFLON SC-383, SURFLON S-393, and SURFLON
KH-40 (manufactured by ASAHI GLASS CO., LTD.), PF636, PF656,
PF6320, PF6520, and PF7002 (manufactured by OMNOVA Solutions Inc.),
and the like.
[0333] As the fluorine-based surfactant, a block polymer can also
be used. For example, the compounds described in JP2011-089090A can
also be used, and the content of the document is incorporated into
the present specification.
[0334] <Solvent>
[0335] It is preferable that the curable composition contains a
solvent. As the solvent, known solvents can be used without
particular limitation.
[0336] The content of the solvent in the curable composition is not
particularly limited. Generally, the content of the solvent is
preferably adjusted such that the content becomes 20% to 90% by
mass with respect to the solid contents of the curable composition,
and more preferably adjusted such that the content becomes 25% to
50% by mass with respect to the solid contents of the curable
composition.
[0337] One kind of solvent may be used singly, or two or more kinds
of solvents may be used in combination. In a case where two or more
kinds of solvents are used in combination, it is preferable that
the content thereof is adjusted such that the total solid content
of the curable composition falls into the above range.
[0338] Examples of the solvent include water and an organic
solvent.
[0339] Examples of the organic solvent include acetone, methyl
ethyl ketone, cyclohexane, ethyl acetate, ethylene dichloride,
tetrahydrofuran, toluene, ethylene glycol monomethyl ether,
ethylene glycol monoethyl ether, ethylene glycol dimethyl ether,
propylene glycol monomethyl ether, propylene glycol monoethyl
ether, acetyl acetone, cyclohexanone, cyclopentanone, diacetone
alcohol, ethylene glycol monomethyl ether acetate, ethylene glycol
ethyl ether acetate, ethylene glycol monoisopropyl ether, ethylene
glycol monobutyl ether acetate, 3-methoxypropanol, methoxymethoxy
ethanol, diethylene glycol monomethyl ether, diethylene glycol
monoethyl ether, diethylene glycol dimethyl ether, diethylene
glycol diethyl ether, propylene glycol monomethyl ether acetate,
propylene glycol monoethyl ether acetate, 3-methoxypropyl acetate,
N,N-dimethylformamide, dimethyl sulfoxide, .gamma.-butyrolactone,
butyl acetate, methyl lactate, N-methyl-2-pyrrolidone, ethyl
lactate, and the like, but the present invention is not limited to
these.
[0340] <Colorant>
[0341] The curable composition may contain a colorant. In the
present specification, the colorant means a compound different from
inorganic particles. Particularly, a metal complex pigment (for
example, Pigment Yellow 117, 129, 150, 153, or the like which will
be described later) is classified as an organic pigment and is not
included in the inorganic particles described above.
[0342] As the colorant, various known pigments (coloring pigments)
and dyes (coloring dyes) can be used. Examples of the pigments
include organic pigments.
[0343] In a case where the curable composition contains a colorant,
the content of the colorant can be determined according to the
optical characteristics of the cured film to be obtained.
Furthermore, one kind of colorant may be used singly, or two or
more kinds of colorants may be used in combination.
[0344] Organic Pigment
[0345] Examples of organic pigments include Color Index (C. I.)
Pigment Yellow 1, 2, 3, 4, 5, 6, 10, 11, 12, 13, 14, 15, 16, 17,
18, 20, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 42, 43,
53, 55, 60, 61, 62, 63, 65, 73, 74, 77, 81, 83, 86, 93, 94, 95, 97,
98, 100, 101, 104, 106, 108, 109, 110, 113, 114, 115, 116, 117,
118, 119, 120, 123, 125, 126, 127, 128, 129, 137, 138, 139, 147,
148, 150, 151, 152, 153, 154, 155, 156, 161, 162, 164, 166, 167,
168, 169, 170, 171, 172, 173, 174, 175, 176, 177, 179, 180, 181,
182, 185, 187, 188, 193, 194, 199, 213, 214, and the like,
[0346] C. I. Pigment Orange 2, 5, 13, 16, 17:1, 31, 34, 36, 38, 43,
46, 48, 49, 51, 52, 55, 59, 60, 61, 62, 64, 71, 73, and the
like,
[0347] C. I. Pigment Red 1, 2, 3, 4, 5, 6, 7, 9, 10, 14, 17, 22,
23, 31, 38, 41, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 52:1, 52:2,
53:1, 57:1, 60:1, 63:1, 66, 67, 81:1, 81:2, 81:3, 83, 88, 90, 105,
112, 119, 122, 123, 144, 146, 149, 150, 155, 166, 168, 169, 170,
171, 172, 175, 176, 177, 178, 179, 184, 185, 187, 188, 190, 200,
202, 206, 207, 208, 209, 210, 216, 220, 224, 226, 242, 246, 254,
255, 264, 270, 272, 279, and the like;
[0348] C. I. Pigment Green 7, 10, 36, 37, 58, 59, and the like;
[0349] C. I. Pigment Violet 1, 19, 23, 27, 32, 37, 42, and the
like;
[0350] C. I. Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6,
16, 22, 60, 64, 66, 79, 80, and the like. One kind of pigment may
be used singly, or two or more kinds of pigments may be used in
combination.
[0351] (Dye)
[0352] As the dye, for example, it is possible to use the coloring
agents disclosed in JP1989-090403A (JP-S64-090403A), JP1989-091102A
(JP-S64-091102A), JP1989-094301A (JP-H01-094301A), JP1994-011614A
(JP-H06-011614A), JP2592207B, U.S. Pat. Nos. 4,808,501A,
5,667,920A, US05/059,50A, JP1993-333207A (JP-H05-333207A),
JP1994-035183A (JP-H06-035183A), JP1994-051115A (JP-H06-051115A),
JP1994-194828A (JP-H06-194828A), and the like. The contents of the
above documents are incorporated into the present
specification.
[0353] As dyes sorted based on the chemical structure, it is
possible to use a pyrazole azo compound, a pyrromethene compound,
an anilinoazo compound, a triphenylmethane compound, an
anthraquinone compound, a benzylidene compound, an oxonol compound,
a pyrazolotriazole azo compound, a pyridone azo compound, a cyanine
compound, a phenothiazine compound, a pyrrolopyrazole azomethine
compound, and the like. Furthermore, a coloring agent multimer may
also be used. Examples of the coloring agent multimer include the
compounds described in JP2011-213925A and JP2013-041097A. In
addition, a polymerizable dye containing a polymerizable group in a
molecule can also be used, and examples thereof include commercial
products such as an RDW series manufactured by Wako Pure Chemical
Industries, Ltd.
[0354] (Infrared Absorber)
[0355] The aforementioned colorant may further contain an infrared
absorber. The infrared absorber means a component different from
the inorganic particles described above.
[0356] In the present specification, the infrared absorber means a
compound absorbing light having a wavelength in an infrared range
(preferably at a wavelength of 650 to 1,300 nm). The infrared
absorber is preferably a compound having a maximum absorption
wavelength in a range of a wavelength of 675 to 900 nm.
[0357] Examples of compounds having such spectral characteristics
include a pyrrolopyrrole compound, a copper compound, a cyanine
compound, a phthalocyanine compound, an iminium compound, a thiol
complex-based compound, a transition metal oxide-based compound, a
squarylium compound, a naphthalocyanine compound, a quaterrylene
compound, a dithiol metal complex-based compound, a croconium
compound, and the like.
[0358] As the phthalocyanine compound, the naphthalocyanine
compound, the iminium compound, the cyanine compound, the
squarylium compound, and the croconium compound, the compounds
described in paragraphs "0010" to "0081" in JP2010-111750A can also
be used, and the contents of the paragraphs are incorporated into
the present specification. Regarding the cyanine compound, for
example, "Functional Dyes, Makoto Okawara/Masaru Matsuoka/Teijiro
Kitao/Tsuneaki Hirashima, Kodansha Scientific Ltd." can be referred
to, and the content of this document is incorporated into the
present specification.
[0359] As the colorant having the spectral characteristics
described above, it is possible to use the compound described in
paragraphs "0004" to "0016" in JP1995-164729A (JP-H07-164729A), the
compound described in paragraphs "0027" to "0062" in
JP2002-146254A, and the near-infrared absorption particles
described in paragraphs "0034" to "0067" in JP2011-164583A that are
formed of crystallites of an oxide containing Cu and/or P and have
a number-average aggregated particle diameter of 5 to 200 nm. The
contents of the paragraphs are incorporated into the present
specification.
[0360] As the compound having a maximum absorption wavelength in a
range of a wavelength of 675 to 900 nm, at least one kind of
compound selected from the group consisting of a cyanine compound,
a pyrrolopyrrole compound, a squarylium compound, a phthalocyanine
compound, and a naphthalocyanine compound is preferable.
[0361] Furthermore, the infrared absorber is preferably a compound
which dissolves in an amount equal to or greater than 1% by mass in
water at 25.degree. C., and more preferably a compound which
dissolves in an amount equal to or greater than 10% by mass in
water at 25.degree. C. In a case where such a compound is used,
solvent resistance becomes excellent.
[0362] Regarding the pyrrolopyrrole compound, paragraphs "0049" to
"0062" in JP2010-222557A can be referred to, and the contents of
the paragraphs are incorporated into the present specification.
Regarding the cyanine compound and the squarylium compound,
paragraphs "0022" to "0063" in WO2014/088063A, paragraphs "0053" to
"0118" in WO2014/030628A, paragraphs "0028" to "0074" in
JP2014-059550A, paragraphs "0013" to "0091" in WO2012/169447A,
paragraphs "0019" to "0033" in JP2015-176046A, paragraphs "0053" to
"0099" in JP2014-063144A, paragraphs "0085" to "0150" in
JP2014-052431A, paragraphs "0076" to "0124" in JP2014-044301A,
paragraphs "0045" to "0078" in JP2012-008532A, paragraphs "0027" to
"0067" in JP2015-172102A, paragraphs "0029" to "0067" in
JP2015-172004A, paragraphs "0029" to "0085" in JP2015-040895A,
paragraphs "0022" to "0036" in JP2014-126642A, paragraphs "0011" to
"0017" in JP2014-148567A, paragraphs "0010" to "0025" in
JP2015-157893A, paragraphs "0013" to "0026" in JP2014-095007A,
paragraphs "0013" to "0047" in JP2014-080487A, paragraphs "0007" to
"0028" in JP2013-227403A, and the like can be referred to, and the
contents of the paragraphs are incorporated into the present
specification.
[0363] The content of the colorant in the curable composition is
not particularly limited, but is preferably 0.0001% to 70% by mass
with respect to the total solid content of the curable composition
in general. One kind of colorant may be used singly, or two or more
kinds of colorants may be used in combination. In a case where two
or more kinds of colorants are used in combination, the total
content thereof is within the above range.
[0364] <Ultraviolet Absorber>
[0365] The curable composition may contains an ultraviolet
absorber. In a case where the curable composition contains an
ultraviolet absorber, a cured film obtained from the composition
has a better pattern shape (finer pattern shape).
[0366] As the ultraviolet absorber, it is possible to use
ultraviolet absorbers based on salicylate, benzophenone,
benzotriazole, substituted acrylonitrile, triazine, and the
like.
[0367] For examples, as the ultraviolet absorber, the compounds
described in paragraphs "0137" to "0142" in JP2012-068418A
(paragraphs "0251" to "0254" in US2012/0068292A corresponding to
JP2012-068418A) can be used, and the contents of the paragraphs can
be adopted and incorporated into the present specification.
[0368] In addition, a diethylamino-phenylsulfonyl-based ultraviolet
absorber (manufactured by DAITO CHEMICAL CO., LTD., trade name:
UV-503) and the like can also be used.
[0369] As the ultraviolet absorber, the compounds described in
paragraphs "0134" to "0148" in JP2012-032556A can also be used, and
the contents of the paragraphs are incorporated into the present
specification.
[0370] The content of the ultraviolet absorber in the curable
composition is not particularly limited. Generally, the content of
the ultraviolet absorber with respect to the total solid content of
the curable composition is preferably 0.001% to 15% by mass, more
preferably 0.01% to 10% by mass, and even more preferably 0.1% to
5% by mass.
[0371] <Silane Coupling Agent>
[0372] The curable composition may contain a silane coupling
agent.
[0373] In the present specification, the silane coupling agent
means a compound containing the following hydrolyzable group and
other functional groups in a molecule. The hydrolyzable group
refers to a substituent which is directly bonded to a silicon atom
and can form a siloxane bond by a hydrolysis reaction and/or a
condensation reaction. Examples of the hydrolyzable group include a
halogen atom, an alkoxy group, an acyloxy group, and an alkenyloxy
group directly bonded to a silicon atom. In a case where the
hydrolyzable group contains carbon atoms, the number of carbon
atoms is preferably equal to or smaller than 6, and more preferably
equal to or smaller than 4. Particularly, an alkoxy group having 4
or less carbon atoms or an alkenyloxy group having 4 or less carbon
atoms is preferable.
[0374] It is preferable that the silane coupling agent contains
none of the silicon atoms and fluorine atoms other than the silicon
atom bonded to the hydrolyzable group. In a case where a cured film
is formed on a substrate by using the curable composition
containing the silane coupling agent, the cured film exhibits
higher adhesiveness with respect to the substrate.
[0375] In the curable composition, the content of the silane
coupling agent with respect to the total solid content in the
curable composition is preferably 0.1% to 10% by mass, more
preferably 0.5% to 8% by mass, and even more preferably 1.0% to 6%
by mass.
[0376] One kind of silane coupling agent may be used singly, or two
or more kinds of silane coupling agents may be used in combination.
In a case where two or more kinds of silane coupling agents are
used in combination, the total content thereof is preferably within
the above range.
[0377] [Manufacturing Method of Curable Composition]
[0378] The curable composition can be prepared by mixing together
the aforementioned components by known mixing methods (for example,
mixing methods using a stirrer, a homogenizer, a high-pressure
emulsification device, a wet-type pulverizer, a wet-type disperser,
and the like). At the time of preparing the curable composition,
the components may be mixed together at once. Alternatively, each
of the components may be dissolved or dispersed in a solvent, and
then sequentially mixed together. The order of components mixed in
and the operation conditions are not particularly limited.
[0379] For the purpose of removing foreign substances, reducing
defects, and the like, it is preferable that the curable
composition is filtered through a filter. As the filter, known
filters can be used without particular limitation.
[0380] The material of the filter is not particularly limited. For
example, the filter may be formed of a fluororesin such as
polytetrafluoroethylene (PTFE), a polyamide-based resin such as
nylon, and a polyolefin-based resin such as polyethylene or
polypropylene (PP). Among these, a filter formed of polypropylene
(including high-density polypropylene) or nylon is preferable.
[0381] The pore size of the filter is not particularly limited.
Generally, the pore size is preferably 0.1 to 7.0 .mu.m, more
preferably 0.2 to 2.5 .mu.m, even more preferably 0.2 to 1.5 .mu.m,
and particularly preferably 0.3 to 0.7 .mu.m. In a case where the
pore size is within the above range, it is possible to reliably
remove fine foreign substances such as impurities and aggregates
contained in the pigment while preventing the inorganic particles
(containing metal carbide-containing particles) from clogging the
filter.
[0382] At the time of using filters, different filters may be used
in combination. At this time, filtering performed using a first
filter may be carried out only once or twice or more. In a case
where filtering is performed twice or more by using a combination
of different filters, the pore size of the filter used in the
second filtering is preferably the same as or larger than the pore
size of the filter used in the first filtering. In addition,
filters formed of the same material and having different pore sizes
may be combined. Regarding the pore size, the nominal pore size of
the filter manufacturer can be referred to.
[0383] Examples of commercial filters include filters from Pall
Corporation Japan, Advantac Toyo Kaisha, Ltd., Nihon Entegris K.K.
(former MICRONIX JAPAN CO., LTD.), KITZ MICRO FILTER CORPORATION,
and the like.
[0384] As a second filter, a filter formed of the same material as
the first filter described above and the like can be used. The pore
size of the second filter is not particularly limited. Generally,
the pore size of the second filter is preferably 0.2 to 10.0 .mu.m,
more preferably 0.2 to 7.0 .mu.m, and even more preferably 0.3 to
6.0 .mu.m.
[0385] It is preferable that the curable composition substantially
does not contain impurities such as a metal (particles and ions), a
metal salt containing halogen, an acid, and an alkali. In the
present specification, "substantially does not contain" means that
the impurities are undetectable by the following measurement
method.
[0386] The content of the impurity contained in the curable
composition, the aforementioned components, the aforementioned
filter, and the like is not particularly limited. The content of
the impurity with respect to the total mass of each of the curable
composition, the aforementioned component, the aforementioned
filter, and the like is preferably equal to or smaller than 1 mass
ppm, more preferably equal to or smaller than 1 mass ppb, even more
preferably equal to or smaller than 100 mass ppt, and particularly
preferably equal to or smaller than 10 mass ppt. It is most
preferable that the curable composition, the aforementioned
components, the aforementioned filter, and the like substantially
do not contain the impurity.
[0387] The content of the impurity can be measured using an
inductively coupled plasma mass spectrometer (manufactured by
Yokogawa Analytical Systems, Inc., Agilent 7500cs model).
[0388] ppm represents parts per million, ppb represents parts per
billion, and ppt represents parts per trillion.
[0389] [Cured Film and Manufacturing Method of Cured Film]
[0390] The cured film according to an embodiment of the present
invention is a cured film obtained by curing the aforementioned
curable composition. The thickness of the cured film is not
particularly limited, but is preferably 0.2 to 7 .mu.m and more
preferably 0.4 to 5 .mu.m in general.
[0391] The aforementioned thickness is an average thickness which
is a value determined by measuring the thickness of the cured film
at any 5 or more sites and calculating an arithmetic mean
thereof.
[0392] The manufacturing method of the cured film is not
particularly limited, and examples thereof include a method of
coating a substrate with the curable composition so as to form a
coating film and performing a curing treatment on the coating film
so as to manufacturing a cured film.
[0393] The method of the curing treatment is not particularly
limited, and examples thereof include a photocuring treatment and a
thermal curing treatment. In view of easily forming a pattern, a
photocuring treatment (particularly, a curing treatment performed
by irradiation with actinic rays or radiation) is preferable.
[0394] The cured film according to the embodiment of the present
invention is a cured film obtained by curing a curable composition
layer formed using the curable composition.
[0395] The manufacturing method of the cured film is not
particularly limited, but preferably includes the following
steps.
[0396] Curable composition layer forming step
[0397] Exposure step
[0398] Development step
[0399] Hereinafter, each of the steps will be described.
[0400] <Curable Composition Layer Forming Step>
[0401] The curable composition layer forming step is a step of
forming a curable composition layer by using the curable
composition. Examples of the step of forming a curable composition
layer by using the curable composition include a step of coating a
substrate with the curable composition so as to form a curable
composition layer.
[0402] The type of the substrate is not particularly limited. In a
case where the substrate is used in a solid-state imaging element,
examples of the substrate include a silicon substrate. In a case
where the substrate is used in a color filter (including a color
filter for a solid-state imaging element), examples of the
substrate include a glass substrate (glass wafer), and the
like.
[0403] As the method for coating a substrate with the curable
composition, it is possible to use various coating methods such as
spin coating, slit coating, injection method, spray coating, spin
coating, cast coating, roll coating, and a screen printing
method.
[0404] The curable composition with which the substrate is coated
is generally formed into a curable composition layer by being dried
under the condition of a temperature of 70.degree. C. to
150.degree. C. for about 1 to 4 minutes.
[0405] <Exposure Step>
[0406] In the exposure step, the curable composition layer formed
in the curable composition layer forming step is subjected to
exposure by being irradiated with actinic rays or radiation through
a photomask comprising a pattern-like opening portion such that
only the curable composition layer irradiated with light is
cured.
[0407] It is preferable to perform exposure by the irradiation of
radiation. It is preferable to use ultraviolet rays such as g-line,
h-line, and i-line. As a light source, a high-pressure mercury lamp
is preferable. The irradiation intensity is not particularly
limited, but is preferably 5 to 1,500 mJ/cm.sup.2 and more
preferably 10 to 1,000 mJ/cm.sup.2in general.
[0408] <Development Step>
[0409] After the exposure step, a development treatment
(development step) is performed such that a portion not being
irradiated with light in the exposure step is eluted in a
developer. In this way, only a portion cured by light remains on
the substrate.
[0410] The developer is not particularly limited, and examples
thereof include alkaline developers. Among these, an organic
alkaline developer is preferable.
[0411] The development conditions are not particularly limited. The
development temperature is generally preferably 20.degree. C. to
40.degree. C., and the development time is generally preferably 20
to 180 seconds.
[0412] The aqueous alkaline solution (alkaline developer) is not
particularly limited. Examples of alkaline compounds to be
incorporated into inorganic alkaline developers include sodium
hydroxide, potassium hydroxide, sodium carbonate, sodium hydrogen
carbonate, sodium silicate, sodium metasilicate, and the like.
[0413] The content of the above compound in the aqueous alkaline
solution is not particularly limited. Generally, the content of the
above compound with respect to the total mass of the aqueous
alkaline solution is preferably 0.001% to 10% by mass, and more
preferably 0.005% to 0.5% by mass.
[0414] Examples of alkaline compounds incorporated into the organic
alkaline developers include ammonia, ethylamine, diethylamine,
dimethylethanolamine, tetramethylammonium hydroxide,
tetraethylammonium hydroxide, tetrapropylammonium hydroxide,
tetrabutylammonium hydroxide, benzyltrimethylammonium hydroxide,
choline, pyrrole, piperidine, 1,8-diazabicyclo-[5,4,0]-7-undecen,
and the like.
[0415] The content of the above compound in the aqueous alkaline
solution is not particularly limited. Generally, the content of the
above compound with respect to the total mass of the aqueous
alkaline solution is preferably 0.001% to 10% by mass, and more
preferably 0.005% to 0.5% by mass.
[0416] The aqueous alkaline solution may contain a water-soluble
organic solvent such as methanol or ethanol. Furthermore, the
aqueous alkaline solution may contain a surfactant.
[0417] In a case where the aqueous alkaline solution described
above is used as a developer, it is preferable to rinse the cured
film with pure water after development.
[0418] The manufacturing method of a cured film may further include
other steps.
[0419] Those other steps are not particularly limited, and can be
appropriately selected according to the purpose.
[0420] Examples of those other steps include a substrate surface
treatment step, a pre-baking step, a post-baking step, and the
like.
[0421] The heating temperature in the pre-baking step and the
post-baking step is not particularly limited, but is preferably
80.degree. C. to 300.degree. C. in general.
[0422] The heating time in the pre-baking step and the post-baking
step is not particularly limited, but is preferably 30 to 300
seconds.
[0423] [Physical Properties of Cured Film]
[0424] OD(Optical Density)
[0425] In view of obtaining better light blocking properties, an
optical density (OD) of the cured film per film thickness of 1.0
.mu.m in a wavelength range of 320 to 1,200 nm is preferably equal
to or higher than 2.0, more preferably equal to or higher than 3.0,
and even more preferably equal to or higher than 4.0. The upper
limit of OD is not particularly limited, but is preferably equal to
or lower than 10 in general.
[0426] In the present specification, the optical density means a
value measured by the method described in Examples. Furthermore, in
the present specification, having an optical density equal to or
higher than 3.0 per film thickness of 1.0 .mu.m in a wavelength
range of 320 to 1,200 nm means that the optical density is equal to
or higher than 3.0 per film thickness of 1.0 .mu.m in the entire
range of a wavelength of 320 to 1,200 nm.
[0427] It is preferable that the cured film has a rough surface
structure. In a case where the cured film has a rough surface
structure, the light reflectivity of the cured film can be reduced.
The cured film may have a rough structure on a surface thereof.
Alternatively, a coating film may be disposed on the cured film so
as to impart a rough structure. The shape of the rough surface
structure is not particularly limited, but it is preferable that
the surface roughness thereof is within a range of 0.55 to equal to
or lower than 1.5 .mu.m.
[0428] The light reflectivity of the cured film is preferably equal
to or lower than 5%, more preferably equal to or lower than 3%, and
even more preferably equal to or lower than 2%.
[0429] The method for preparing the rough surface structure is not
particularly limited, and examples thereof include a method of
incorporating an organic filler and/or an inorganic filler into the
cured film or a coating film; a method of roughening the surface of
the cured film and/or a coating film by means of a lithography
method, an etching method, a sputtering method, or a nanoimprinting
method; and the like.
[0430] Examples of the method for reducing the light reflectivity
of the cured film include a method of disposing a film of low
refractive index on the cured film; a method of disposing a film
having a different refractive index (for example, a film of high
refractive index) on a film of low refractive index; and a method
of forming a low-optical-density layer and a high-optical-density
layer described in JP2015-001654A for example.
[0431] The cured film is suitable for a light blocking member, a
light blocking film, an antireflection member, and an
antireflection film of optical filters and modules used in portable
instruments such as a personal computer, a tablet PC, a mobile
phone, a smartphone, and a digital camera; office automation (OA)
instruments such as a printer composite machine and a scanner;
industrial instruments such as monitoring camera, a barcode reader,
an automated teller machine (ATM), a high-speed camera, an
instrument having a personal authentication function exploiting
face image recognition; camera instruments for automobile use;
medical camera instruments such as an endoscope, a capsule
endoscope, and a catheter; a biometric sensor, a military
reconnaissance camera, a camera for a three-dimensional map, a
camera for observing weather and sea, a camera for land resource
investigation, space instruments such as an exploration camera for
the astronomy of the universe and a deep space target; and the
like.
[0432] The cured film can also be used in a micro light emitting
diode (LED), a micro organic light emitting diode (OLED), and the
like. The cured film is suitable for an optical filter and an
optical film used in the micro LED and the micro OLED and for a
member to which a light blocking function or an antireflection
function is to be imparted.
[0433] Examples of the micro LED and the micro OLED include those
described in JP2015-500562A and JP2014-533890A.
[0434] The cured film is suitable as an optical filter and an
optical film used in a quantum dot display. Furthermore, the cured
film is suitable as a member to which a light blocking function or
an antireflection function is to be imparted.
[0435] Examples of the quantum dot display include those described
in US2013/0335677A, US2014/0036536A, US2014/0036203A, and
US2014/0035960A.
[0436] [Solid-State Imaging Device and Solid-State Imaging
Element]
[0437] The solid-state imaging device and the solid-state imaging
element according to an embodiment of the present invention include
the cured film described above. The aspect in which the solid-state
imaging element includes the cured film is not particularly
limited. For example, a constitution may be adopted in which a
plurality of photodiodes and light-receiving elements formed of
polysilicon or the like constituting a light-receiving area of a
solid-state imaging element (a CCD image sensor, a CMOS image
sensor, or the like) are provided on a substrate, and solid-state
imaging element comprises the cured film on a surface side of a
support on which the light-receiving elements are formed (for
example, a portion other than light-receiving portions and/or
pixels for adjusting color, and the like) or on a side opposite to
the surface on which the light-receiving elements are formed.
[0438] The solid-state imaging device includes the aforementioned
solid-state imaging element.
[0439] Examples of the constitutions of the solid-state imaging
device and the solid-state imaging element will be described with
reference to FIG. 1 and FIG. 2. In FIG. 1 and FIG. 2, in order that
each portion is clearly seen, some portions are magnified in
disregard of a thickness ratio and/or a width ratio between the
portions.
[0440] As shown in FIG. 1, a solid-state imaging device 100
comprises a rectangular solid-state imaging element 101 and a
transparent cover glass 103 which is held above the solid-state
imaging element 101 and seals the solid-state imaging element 101.
Furthermore, on the cover glass 103, a lens layer 111 is superposed
through a spacer 104. The lens layer 111 is constituted with a
support 113 and a lens material 112. The lens layer 111 may be
constituted with the support 113 and the lens material 112 that are
integrally formed. In a case where stray light comes into the
peripheral region of the lens layer 111, due to the diffusion of
light, a light condensing effect of the lens material 112 is
weakened. Accordingly, the light reaching an imaging portion 102 is
reduced, and noise occurs due to the stray light. Therefore, a
light blocking film 114 is provided in the peripheral region of the
lens layer 111 such that light is blocked. The cured film according
to the embodiment of the present invention can also be used as the
light blocking film 114.
[0441] The solid-state imaging element 101 performs photoelectric
conversion on an optical image formed on the imaging portion 102,
which becomes a light-receiving surface of the solid-state imaging
element 101, and outputs the converted optical image as an image
signal. The solid-state imaging element 101 comprises a laminated
substrate 105 obtained by laminating two sheets of substrates. The
laminated substrate 105 is formed of a chip substrate 106 and a
circuit substrate 107 that are rectangular substrates having the
same size. The circuit substrate 107 is laminated on the rear
surface of the chip substrate 106.
[0442] As the material of the substrate used as the chip substrate
106, known materials can be used without particular limitation.
[0443] The imaging portion 102 is provided in the central portion
of the surface of the chip substrate 106. In a case where stray
light comes into the peripheral region of the imaging portion 102,
a dark current (noise) occurs from the circuit in the peripheral
region. Therefore, the peripheral region is provided with a light
blocking film 115 such that light is blocked. The cured film
according to the embodiment of the present invention can also be
used as the light blocking film 115.
[0444] A plurality of electrode pads 108 are provided at the edge
of the surface of the chip substrate 106. The electrode pads 108
are electrically connected to the imaging portion 102 through a
signal line (a bonding wire can also be used) not shown in the
drawing that is provided on the surface of the chip substrate
106.
[0445] On the rear surface of the circuit substrate 107, external
connection terminals 109 are provided approximately in positions
below the electrode pads 108. The external connection terminals 109
are connected to the electrode pads 108 through a penetration
electrode 110 vertically penetrating the laminated substrate 105.
Furthermore, the external connection terminals 109 are connected to
a control circuit controlling the driving of the solid-state
imaging element 101, an image processing circuit performing image
processing on an imaging signal output from the solid-state imaging
element 101, and the like through wiring not shown in the
drawing.
[0446] As shown in FIG. 2, the imaging portion 102 is constituted
with the portions provided on a substrate 204 such as a
light-receiving element 201, a color filter 202, and a microlens
203. The color filter 202 has a blue pixel 205b, a red pixel 205r,
a green pixel 205g, and a black matrix 205bm. The cured film
according to the embodiment of the present invention can also be
used as the black matrix 205bm.
[0447] As the material of the substrate 204, the same material as
that of the chip substrate 106 can be used. On the surface layer of
the substrate 204, a p-well layer 206 is formed. In the p-well
layer 206, the light-receiving elements 201, which are formed of an
n-type layer and generate and accumulate signal charges by
photoelectric conversion, are arranged in the form of square
grids.
[0448] On one lateral side of each light-receiving element 201,
through a reading gate portion 207 on the surface layer of the
p-well layer 206, a vertical electric charge transfer path 208
formed of an n-type layer is formed. Furthermore, on the other
lateral side of each light-receiving element 201, through an
element separation region 209 formed of a p-type layer, a vertical
electric charge transfer path 208 belonging to the adjacent pixel
is formed. The reading gate portion 207 is a channel region for the
signal charges accumulated in the light-receiving element 201 to be
read toward the vertical electric charge transfer path 208.
[0449] On the surface of the substrate 204, a gate insulating film
210 formed of an oxide-nitride-oxide (ONO) film is formed. On the
gate insulating film 210, vertical electric charge transfer
electrodes 211 formed of polysilicon or amorphous silicon are
formed to cover the portions which are approximately immediately
above the vertical electric charge transfer path 208, the reading
gate portion 207, and the element separation region 209. The
vertical electric charge transfer electrodes 211 function as
driving electrodes for driving the vertical electric charge
transfer path 208 and performing charge transfer and as reading
electrodes for driving the reading gate portion 207 and reading out
signal charges. The signal charges are transferred to a horizontal
electric charge transfer path and an output portion (floating
diffusion amplifier), which are not shown in the drawing, in this
order from the vertical electric charge transfer path 208 and then
output as voltage signals.
[0450] On each of the vertical electric charge transfer electrodes
211, a light blocking film 212 is formed to cover the surface of
the electrode. The light blocking film 212 has an opening portion
in a position immediately above the light-receiving element 201 and
shields a region other than the opening portion from light. The
cured film according to the embodiment of the present invention can
also be used as the light blocking film 212.
[0451] On the light blocking film 212, a transparent interlayer is
provided which is formed of an insulating film 213 formed of
borophosphosilicate glass (BPSG), an insulating film (passivation
film) 214 formed of P--SiN, and a planarization film 215 formed of
a transparent resin or the like. The color filter 202 is formed on
the interlayer.
[0452] [Black Matrix]
[0453] The black matrix includes the cured film according to the
embodiment of the present invention. The black matrix is
incorporated into a color filter, a solid-state imaging element,
and a liquid crystal display device in some cases.
[0454] Examples of the black matrix include those described above;
a black rim provided in the peripheral portion of a display device
such as a liquid crystal display device; a grid-like and/or a
stripe-like black portion between pixels of red, blue, and green; a
dot-like and/or a linear black pattern for shielding a thin film
transistor (TFT) from light; and the like. The definition of the
black matrix is described in, for example, Yasuhira Kanno,
"Glossary of Liquid Crystal display Manufacturing Device", 2.sup.nd
edition, NIKKAN KOGYO SHIMBUN, LTD., 1996, p. 64.
[0455] In order to improve the display contrast and to prevent
image quality deterioration resulting from current leak of light in
the case of an active matrix driving-type liquid crystal display
device using a thin film transistor (TFT), it is preferable that
the black matrix has high light blocking properties (it is
preferable that the optical density OD is higher than 3).
[0456] The manufacturing method of the black matrix is not
particularly limited, and the black matrix can be manufactured by
the same method as the manufacturing method of the cured film
described above. Specifically, by coating a substrate with the
curable composition so as to form a curable composition layer and
performing exposure and development, a pattern-like cured film
(black matrix) can be manufactured. The film thickness of the cured
film used as the black matrix is preferably 0.1 to 4.0 .mu.m.
[0457] The material of the substrate is not particularly limited,
but it is preferable that the material has a transmittance equal to
or higher than 80% for visible light (wavelength: 400 to 800 nm).
Specifically, examples of such a material include glass such as
soda lime glass, alkali-free glass, quartz glass, and borosilicate
glass; plastic such as a polyester-based resin and a
polyolefin-based resin; and the like. From the viewpoint of
chemical resistance and heat resistance, alkali-free glass, quartz
glass, or the like is preferable.
[0458] [Color Filter]
[0459] The color filter according to an embodiment of the present
invention includes a cured film.
[0460] The aspect in which the color filter includes the cured film
is not particularly limited, and examples thereof include a color
filter comprising a substrate and the aforementioned black matrix.
That is, examples of the color filter include a color filter
comprising colored pixels of red, green, and blue formed on the
opening portion of the black matrix formed on a substrate.
[0461] The color filter including a black matrix (cured film) can
be manufactured, for example, by the following method.
[0462] First, on an opening portion of a pattern-like black matrix
formed on a substrate, a coating film of a resin composition (resin
composition layer) containing pigments corresponding to the colored
pixels of the color filter is formed. As the resin composition for
each color, known resin compositions can be used without particular
limitation. However, it is preferable to use the curable
composition obtained by changing the metal carbide-containing
particles in the curable composition according to the embodiment of
the present invention into colorants corresponding to the
respective pixels.
[0463] Then, the resin composition layer is subjected to exposure
through a photo mask having a pattern corresponding to the opening
portion of the black matrix. Thereafter, an unexposed portion is
removed by a development treatment and then performing baking. In
this way, colored pixels can be formed in the opening portion of
the black matrix. In a case where the series of operations are
performed using, for example, a resin composition for each color
containing red, green, and blue pigments, a color filter having
red, green, and blue pixels can be manufactured.
[0464] [Image Display Device]
[0465] The image display device according to an embodiment of the
present invention includes a cured film. The aspect in which the
image display device (typical examples thereof include a liquid
crystal display device, hereinafter, the liquid crystal display
device will be described) includes the cured film is not
particularly limited, and examples thereof include an aspect in
which the image display device includes a color filter including
the black matrix (cured film) described above.
[0466] Examples of the liquid crystal display device according to
the present embodiment include an aspect in which the liquid
crystal display device comprises a pair of substrates disposed to
face each other and a liquid crystal compound sealed into the space
between the substrates. The substrates are as described above as
the substrate for a black matrix.
[0467] Examples of a specific aspect of the liquid crystal display
device include a laminate having polarizing plate/substrate/color
filter/transparent electrode layer/alignment film/liquid crystal
layer/alignment film/transparent electrode layer/Thin Film
Transistor (TFT) element/substrate/polarizing plate/backlight unit
in this order from the user's side.
[0468] The liquid crystal display device is not limited to the
above, and examples thereof include the liquid crystal display
devices described in "Electronic display device (Akio Sasaki, Kogyo
Chosakai Publishing Co., Ltd., 1990)" and "Display Device (Sumiaki
Ibuki, Sangyo Tosho Publishing Co., Ltd., 1989)" and the liquid
crystal display device described in "Next-Generation Liquid Crystal
Display Technology (Tatsuo Uchida, Kogyo Chosakai Publishing Co.,
Ltd., 1994)".
[0469] [Infrared Sensor]
[0470] The infrared sensor according to an embodiment of the
present invention includes the aforementioned cured film.
[0471] The infrared sensor according to the embodiment will be
described using FIG. 3. In an infrared sensor 300 shown in FIG. 3,
the reference 310 represents a solid-state imaging element.
[0472] The imaging region provided on the solid-state imaging
element 310 is constituted with a combination of an infrared
absorption filter 311 and a color filter 312 according to the
embodiment of the present invention.
[0473] The infrared absorption filter 311 is a film which transmits
light of the range of visible rays (for example, light having a
wavelength of 400 to 700 nm) and blocks light of the infrared range
(for example, light having a wavelength of 800 to 1,300 nm,
preferably having a wavelength of 900 to 1,200 nm, and more
preferably having a wavelength of 900 to 1,000 nm). In the infrared
absorption filter 311, a cured film containing an infrared absorber
(the aspect of the infrared absorber is as described above) as a
colorant can be used.
[0474] The color filter 312 is a color filter in which pixels
transmitting or absorbing light having a specific wavelength in the
range of visible rays are formed. As the color filter 312, for
example, a color filter in which pixels of red (R), green (G), and
blue (B) are formed is used, and the aspect thereof is as described
above.
[0475] Between an infrared transmission filter 313 and the
solid-state imaging element 310, a resin film 314 (for example, a
transparent resin film or the like) is disposed which can transmit
light having a wavelength transmitted through the infrared
transmission filter 313.
[0476] It is preferable that the infrared transmission filter 313
blocks light having a wavelength of 400 to 830 nm and transmits
light having a wavelength of 900 to 1,300 nm, for example.
[0477] On an incidence ray h.nu. side of the color filter 312 and
the infrared transmission filter 313, microlenses 315 are arranged.
A planarization film 316 is formed to cover the microlenses
315.
[0478] Although a resin film 314 is disposed in the embodiment
shown in FIG. 3, the infrared transmission filter 313 may be formed
instead of the resin film 314. That is, on the solid-state imaging
element 310, the infrared transmission filter 313 may be
formed.
[0479] In the embodiment shown in FIG. 3, the film thickness of the
color filter 312 is the same as the film thickness of the infrared
transmission filter 313. However, the film thicknesses may be
different from each other.
[0480] In the embodiment shown in FIG. 3, the color filter 312 is
provided to be closer to the incidence ray h.nu. side than the
infrared absorption filter 311. However, the order of the infrared
absorption filter 311 and the color filter 312 may be switched such
that the infrared absorption filter 311 is provided to be closer to
the incidence ray h.nu. side than the color filter 312.
[0481] In the embodiment shown in FIG. 3, the infrared absorption
filter 311 and the color filter 312 are laminated to be adjacent to
each other. However, these filters do not need to be adjacent to
each other, and another layer may be provided between the filters.
The cured film according to the embodiment of the present invention
can be used as a light blocking film on the edge of the surface of
the infrared absorption filter 311 or lateral surface of the
infrared absorption filter 311. Furthermore, by being used as a
device inner wall of an infrared sensor, the cured film according
to the embodiment of the present invention can prevent internal
reflection or unintended incidence of light on the light receiving
portion and can improve sensitivity.
[0482] According to the infrared sensor, image information can be
simultaneously input. Therefore, motion sensing by which a subject
whose movement is to be detected is recognized can be carried out.
Furthermore, because distance information can be obtained, images
including 3D information and the like can be captured.
[0483] Next, a solid-state imaging device in which the
aforementioned infrared sensor is used will be described.
[0484] The solid-state imaging device includes a lens optical
system, a solid-state imaging element, an infrared emission diode,
and the like. Regarding each of the constituents of the solid-state
imaging device, paragraphs "0032" to "0036" in JP2011-233983A can
be referred to, and the contents of the paragraphs are incorporated
into the present specification.
EXAMPLES
[0485] Hereinafter, the present invention will be more specifically
described based on examples. The materials, the amount of the
materials used, the proportion of the materials, the treatment
content, the treatment procedure, and the like shown in the
following examples can be appropriately modified as long as the
gist of the present invention is maintained. Accordingly, the scope
of the present invention is not limited to the following
examples.
[0486] [Preparation of Curable Composition]
[0487] The components described in Table 1 were mixed together such
that the content thereof became as described above Table 1, thereby
preparing curable compositions of examples and comparative
examples. The curable compositions were prepared according to the
following procedure.
[0488] First, inorganic particles (metal carbide-containing
particles), a dispersant, and some of organic solvents were mixed
together, and the obtained mixture was dispersed under the
following conditions by using NMP-Pilot manufactured by Shinmaru
Enterprises Corporation., thereby obtaining a dispersed
composition.
[0489] (Dispersion Conditions)
[0490] Bead size: 0.05 mm, (zirconia beads manufactured by NIKKATO
CORPORATION, YTZ)
[0491] Bead filling rate: 65% by volume
[0492] Circumferential speed of mill: 10 m/sec
[0493] Circumferential speed of separator: 13 m/s
[0494] Amount of mixed solution subjected to dispersion treatment:
15 kg
[0495] Circulation flow rate (pump feeding amount): 90 kg/hour
[0496] Treatment solution temperature: 19.degree. C. to 21.degree.
C.
[0497] Coolant: water
[0498] Treatment time: 22 hours
[0499] Then, the aforementioned dispersed composition, an
alkali-soluble resin, a polymerization initiator, a polymerizable
compound, a surfactant, a polymerization inhibitor, and the
remaining organic solvents were mixed together such that the
content of the components became as described in Table 1, thereby
obtaining a curable composition of each of examples and comparative
examples. Details of the components are as below.
[0500] <Inorganic Particles>
[0501] Metal Carbide-Containing Particles
[0502] TaC (average primary particle diameter: 60 nm, synthesized
by RF thermal plasma method)
[0503] TaC (average primary particle diameter: 5 nm, synthesized by
RF thermal plasma method)
[0504] TaC (average primary particle diameter: 200 nm, synthesized
by RF thermal plasma method)
[0505] NbC (average primary particle diameter: 60 nm, synthesized
by RF thermal plasma method)
[0506] VC (average primary particle diameter: 60 nm, synthesized by
RF thermal plasma method)
[0507] Tic (average primary particle diameter: 60 nm, synthesized
by RF thermal plasma method)
[0508] TiN (average primary particle diameter: 60 nm, synthesized
by RF thermal plasma method)
[0509] Other Particles
[0510] SiO.sub.2 (average primary particle diameter: 250 nm,
manufactured by Admatechs., "SO-C1")
[0511] <Dispersant>
[0512] As dispersants, the following dispersants A to D were
used.
[0513] (Synthesis of Dispersant A)
[0514] Synthesis of Macromonomer A-1
[0515] .epsilon.-Caprolactone (1,044.2 g), .delta.-valerolactone
(184.3 g), and 2-ethyl-1-hexanol (71.6 g) were introduced into a
three-neck flask having a volume of 3,000 mL, thereby obtaining a
mixture. Then, the mixture was stirred in a state where nitrogen
was being blown thereinto. Thereafter, Disperbyk 111 (12.5 g,
manufactured by BYKChemie GmbH, phosphoric acid resin) was added to
the mixture, and the obtained mixture was heated to 90.degree. C.
After 6 hours, by .sup.1H-nuclear magnetic resonance (NMR), the
disappearance of a signal resulting from 2-ethyl-1-hexanol in the
mixture was confirmed, and then the mixture was heated to
110.degree. C. In a nitrogen atmosphere, a polymerization reaction
was continued for 12 hours at 110.degree. C., and then by
.sup.1H-NMR, the disappearance of signals resulting from
.epsilon.-caprolactone and .delta.-valerolactone was confirmed. The
molecular weight of the obtained compound was measured by a Gel
permeation chromatography (GPC, under the measurement conditions
which will be described later). After it was confirmed that the
molecular weight of the compound reached a desired value,
2,6-di-t-butyl-4-methylphenol (0.35 g) was added to the mixture
containing the compound, and then 2-methacryloyloxyethyl isocyanate
(87.0 g) was further added dropwise to the obtained mixture for 30
minutes. Six hours after the finish of the dropwise addition, by
.sup.1H-NMR, the disappearance of a signal resulting from
2-methacryloyloxyethyl isocyanate (MOI) was confirmed. Then,
propylene glycol monomethyl ether acetate (PGMEA) (1,387.0 g) was
added to the mixture, thereby obtaining a macromonomer A-1 solution
(2,770 g) having a concentration of 50% by mass. The weight-average
molecular weight of the obtained macromonomer A-1 was 6,000.
[0516] Synthesis of Dispersant A
[0517] The macromonomer A-1 (200.0 g), methacrylic acid
(hereinafter, referred to as "MAA" as well, 60.0 g), benzyl
methacrylate (hereinafter, referred to as "BzMA" as well, 40.0 g),
and PGMEA (propylene glycol 1-monomethyl ether 2-acetate, 366.7 g)
were introduced into a three-neck flask having a volume of 1,000
mL, thereby obtaining a mixture. The mixture was stirred while
nitrogen was being blown thereinto. Then, while nitrogen was being
allowed to flow in the flask, the mixture was heated to 75.degree.
C. Thereafter, dodecyl mercaptan (5.85 g) and 2,2'-azobis(methyl
2-methylpropionate) (1.48 g, hereinafter, referred to as "V-601" as
well) were added in this order to the mixture, and a polymerization
reaction was initiated. The mixture was heated for 2 hours at
75.degree. C., and then V-601 (1.48 g) was added to the mixture.
After 2 hours, V-601 (1.48 g) was further added to the mixture.
After the reaction was performed for 2 hours, the mixture was
heated to 90.degree. C. and stirred for 3 hours. By the above
operation, the polymerization reaction was finished, and a
dispersant A was obtained.
[0518] (Synthesis of Dispersant B)
[0519] Tetrabutylammonium bromide (TBAB, 7.5 g) and p-methoxyphenol
(MEHQ, 0.13 g) were added to the dispersant A synthesized as above,
and then glycidyl methacrylate (hereinafter, referred to as "GMA"
as well, 66.1 g) was added dropwise thereto. After the finish of
the dropwise addition, in the air, the reaction was continued for 7
hours, and the acid value was measured, thereby confirming the
finish of the reaction. By adding PGMEA (643.6 g) to the obtained
mixture, a 20% by mass solution of a dispersant B was obtained. The
weight-average molecular weight of the obtained dispersant B was
35,000, and the acid value of the dispersant B was 50 mgKOH/mg.
[0520] Dispersant C: compound represented by the following formula
(the numerical value on each constitutional unit represents a molar
ratio. That is, a dispersant C contains two kinds of constitutional
units, and the molar ratio between the constitutional units is
39:61.)
##STR00022##
[0521] Dispersant D: compound represented by the following formula
(the numerical value on each constitutional unit represents a molar
ratio. That is, a dispersant D contains two kinds of constitutional
units, and a molar ratio between the constitutional units is
24:76.)
##STR00023##
[0522] <Alkali-Soluble Resin>
[0523] As alkali-soluble resins, A-1 and A-2 described below were
used.
[0524] A-1: "ACRYCURE RD-F8", manufactured by NIPPON SHOKUBAI CO.,
LTD., solid content: 40%, solvent: propylene glycol monomethyl
ether
[0525] A-2: compound synthesized by the following method
[0526] The alkali-soluble resin A-2 was synthesized by the
following method. First, 95.1 g of 4,4'-diaminodiphenylether, 6.2 g
of bis(3-aminopropyl)tetramethyldisiloxane, 525 g of
.gamma.-butyrolactone, and 220 g of N-methyl-2-pyrrolidone were
mixed together, thereby obtaining a mixed solution.
3,3',4,4'-Biphenyltetracarboxylic acid dianhydride (144.1 g) was
added to the mixed solution and reacted for 3 hours at 70.degree.
C., and then 3.0 g of phthalic acid anhydride was added thereto and
reacted for 2 hours at 70.degree. C., thereby obtaining a 25% by
mass alkali-soluble resin A-2 solution (the resin A-2 corresponds
to polyamic acid).
[0527] <Polymerizable Compound>
[0528] As polymerizable compounds, M1 to M4 described below were
used.
[0529] M1: trade name "KAYARAD DPHA", manufactured by Nippon Kayaku
Co., Ltd., (mixture of hexafunctional polymerizable compound
(amount of ethylenically unsaturated group: 10.4 mmol/g) and
pentafunctional polymerizable compound (amount of ethylenically
unsaturated group: 9.5 mmol/g))
[0530] M2: trade name "U-15HA", manufactured by SHIN-NAKAMURA
CHEMICAL CO., LTD., urethane acrylate having 15 functional
groups.
[0531] M3: trade name "KAYARAD RP-1040", manufactured by Nippon
Kayaku Co., Ltd., compound represented by the following formula
##STR00024##
[0532] M4: compound represented by the following formula
(synthesized with reference to
[0533] JP2009-169049A)
##STR00025##
[0534] <Polymerization Initiator>
[0535] As polymerization initiators, I-1 to I-3 described below
were used.
[0536] I-1: compound represented by the following formula
(photopolymerization initiator, corresponding to oxime
compound)
##STR00026##
[0537] I-2: compound represented by the following formula (trade
name "B-CIM", manufactured by Hodogaya Chemical Co., Ltd.,
corresponding to photopolymerization initiator, not corresponding
to oxime compound)
##STR00027##
[0538] I-3: compound represented by the following formula
(corresponding to photopolymerization initiator, not corresponding
to oxime compound)
##STR00028##
[0539] <Surfactant>
[0540] As a surfactant, a compound F-1 represented by the following
formula was used (weight-average molecular weight=15,311). In the
following formula, the structural units represented by (A) and (B)
have a proportion of 62 mol % and 38 mol % respectively. In the
structural unit represented by Formula (B), a, b, and c satisfy the
relationship of a+c=14 and b=17.
##STR00029##
[0541] <Polymerization Inhibitor>
[0542] PI-1: p-methoxyphenol
[0543] <Solvent>
[0544] Propylene glycol monomethyl ether acetate (PGMEA)
[0545] Each of the curable compositions was diluted with PGMEA such
that the solid contents thereof became as described in Table 1.
[0546] [Evaluation]
[0547] The obtained curable compositions were evaluated regarding
the following items.
[0548] [Light Blocking Properties]
[0549] The light blocking properties of the cured film were
evaluated by the following method.
[0550] First, a glass substrate (EagleXG, manufactured by Corning
Incorporated.) having a thickness of 0.7 mm and a size of 10
cm.times.10 cm was coated with each of the curable compositions by
a spin coating method, thereby obtaining a curable composition
layer. At this time, the rotation speed of the spin coater was
adjusted such that the thickness of the curable composition layer
became 1.0 .mu.m after drying. Then, the surface of the glass
substrate was caused to face down, and the glass substrate was
placed on a hot plate and subjected to a heat treatment for 2 hours
at 100.degree. C. such that the curable composition layer was
dried. Thereafter, by using an i-line stepper exposure machine
FPA-3000i5+ (manufactured by Canon Inc.), the curable composition
layer was subjected to exposure at a wavelength of 365 nm in an
exposure amount of 500 mJ/cm.sup.2. Subsequently, the glass
substrate, on which the exposed curable composition layer was
formed, was placed on a horizontally rotating table of a spin
shower development machine (DW-30 model; manufactured by
Chemitronics, Co., Ltd.) and subjected to puddle development for 60
seconds at 23.degree. C. by using CD-2000 (manufactured by FUJIFILM
Electronic Materials Co., Ltd., organic alkaline developer). The
glass substrate having undergone puddle development was fixed to
the horizontally rotating table by a vacuum chuck method. The glass
substrate was rotated at a rotation speed of 50 rpm by a rotation
device, and in this state, pure water was supplied in the form of
shower from a spray nozzle from above the rotation center such that
the wafer was rinsed, thereby obtaining a cured film. By using a
transmission densitometer (X-rite 361T (visual) densitometer), the
optical density (OD) of the obtained cured film at a wavelength of
320 to 1,200 nm was measured. The results were evaluated based on
the following standards.
[0551] A: The minimum OD at the aforementioned wavelength range was
equal to or higher than 4.0.
[0552] B: The minimum OD at the aforementioned wavelength range was
equal to or higher than 3.0 and less than 4.0.
[0553] C: The minimum OD at the aforementioned wavelength range was
equal to or higher than 2.0 and less than 3.0.
[0554] D: The minimum OD at the aforementioned wavelength range was
less than 2.0.
[0555] <Temporal Stability>
[0556] The temporal stability of each of the curable compositions
was evaluated by the following method.
[0557] First, the curable composition was 2.times. diluted with
propylene glycol monomethyl ether acetate, thereby obtaining a
diluted solution. Then, 20 mL of the diluted solution was
collected, and the collected diluted solution was put into a 50 mL
container made of a resin and left to stand for 6 months in an
environment at 23.degree. C. After the diluted solution was left to
stand, 5 g of supernatant 1 cm deep from the level of the diluted
solution in the container made of a resin was collected, and the
amount of solid contents was measured.
[0558] By comparing the amount of solid contents in the supernatant
with the amount of solid contents in each of the just prepared
curable compositions, the amount of change in the amount of solid
contents was calculated. The results were evaluated based on the
following standards. The smaller the amount of change in the amount
of solid contents, the more difficult it is for inorganic particles
to be precipitated in the curable composition.
[0559] The amount of solid contents was calculated by the following
method. That is, 1 g of the curable composition was weighed and
heated for 60 minutes in an oven at 165.degree. C., thereby
obtaining solid contents. The mass of the solid contents was
measured, and the amount of solid contents [% by mass] was
calculated by (mass of solid contents/mass of curable composition
(1 g)).times.100.
[0560] A: The amount of change in the solid content concentration
was less than 1%.
[0561] B: The amount of change in the solid content concentration
was equal to or greater than 1% and less than 3%.
[0562] C: The amount of change in the solid content concentration
was equal to or greater than 3%.
[0563] <Patterning Properties (Development Residues)>
[0564] Each of the curable compositions was stored for 6 months at
23.degree. C., and an electrode pattern of a silicon wafer with a
surface, on which an electrode pattern (copper) was formed, was
spin-coated with each of the curable compositions after storage
such that the film thickness became 0.7 .mu.m after drying, thereby
forming a curable composition layer. Thereafter, the wafer was left
to stand as it was for 10 minutes, and then the silicon wafer on
which the curable composition layer was formed was placed on a hot
plate at 100.degree. C. and heated (baked) for 120 seconds.
Thereafter, by using an i-line stepper exposure machine FPA-3000i5+
(manufactured by Canon Inc.), the curable composition layer was
subjected to exposure through a 2 .mu.m.times.2 .mu.m an Island
pattern mask at a wavelength of 365 nm in an exposure amount of
1,000 mJ/cm.sup.2. Subsequently, the silicon wafer, on which the
exposed curable composition layer was formed, was placed on a
horizontally rotating table of a spin shower development machine
(DW-30 model; manufactured by Chemitronics, Co., Ltd.) and
subjected to puddle development for 60 seconds at 23.degree. C. by
using CD-2000 (manufactured by FUJIFILM Electronic Materials Co.,
Ltd., organic alkaline developer). The silicon wafer having
undergone puddle development was fixed to the horizontally rotating
table by a vacuum chuck method. The silicon wafer was rotated at a
rotation speed of 50 rpm by a rotation device, and in this state,
pure water was supplied in the form of shower from a spray nozzle
from above the rotation center such that the wafer was rinsed.
Then, the rinsed silicon wafer was spray-dried, thereby obtaining a
silicon wafer having a frame-shaped black matrix. For the silicon
wafer obtained as above, by using a scanning electron microscope
(manufactured by Hitachi High-Technologies Corporation, trade name
"SU 8010"), the wafer surface in an unexposed portion was observed
at 20,000.times. magnification, the number of particle-like
residues confirmed in the obtained observation image was counted,
and the patterning properties (development residues) were evaluated
based on the following standards.
[0565] AA: No development residue was observed in the unexposed
portion.
[0566] A: The number of particles-like development residues
observed in the unexposed portion was 1 to 3.
[0567] B: The number of particles-like development residues
observed in the unexposed portion was 4 to 50.
[0568] C: The number of particles-like development residues
observed in the unexposed portion was 51 to 100.
[0569] D: The number of particles-like development residues
observed in the unexposed portion was equal to or greater than
101.
Example 29
[0570] A curable composition was prepared in the same manner as in
Example 2, except that in the curable composition of Example 2, as
other particles (A2), instead of SiO.sub.2, carbon black was used
(trade name "CARBON BLACK S170", manufactured by Degussa AQ average
primary particle diameter: 17 nm, BET (Brunauer, Emmett, Teller)
specific surface area: 200 m.sup.2/g, carbon black manufactured by
gas black method, corresponding to inorganic particles and other
particles, described as "CB" in Table 1).
Example 30
[0571] A curable composition was prepared in the same manner as in
Example 2, except that in the curable composition of Example 2, as
other particles (A2), instead of SiO.sub.2, a colorant was used
(Pigment Yellow 150, manufactured by Hangzhou Star-up Pigment Co.,
Ltd. trade name: 6150 pigment yellow SGN, not corresponding to
inorganic particles, described as "PY150" in Table 1).
TABLE-US-00001 TABLE 1 Components of curable composition Inorganic
particles (A) Metal carbide-contaimng particles (A1) Average
Content in Content Content in primary curable composition (% by
mass) inorganic particle (% by mass) In solid In curable particles
(A) diameter In solid In curable contents composition Type (% by
mass) (nm) contents composition Example 1 51.0 18.3 TaC 100 60 51.0
18.3 Example 2 51.0 18.3 TaC 70 60 35.7 12.8 Example 3 51.0 18.3
TaC 55 60 28.0 10.1 Example 4 56.9 18.3 TaC 100 60 56.9 18.3
Example 5 40.7 18.3 TaC 100 60 40.7 18.3 Example 6 51.0 18.3 TaC
100 60 51.0 18.3 Example 7 51.0 18.3 TaC 100 60 51.0 18.3 Example 8
55.2 18.3 TaC 100 60 55.2 18.3 Example 9 42.4 18.3 TaC 100 60 42.4
18.3 Example 10 51.0 18.3 TaC 100 5 51.0 18.3 Example 11 51.0 18.3
TaC 100 200 51.0 18.3 Example 12 51.0 18.3 NbC 100 60 51.0 18.3
Example 13 51.0 18.3 Vc 100 60 51.0 18.3 Example 14 51.0 18.3 TaC
100 60 51.0 18.3 Example 15 51.0 18.3 TaC 100 60 51.0 18.3 Example
16 55.9 18.3 TaC 100 60 55.9 18.3 Example 17 40.2 18.3 TaC 100 60
40.2 18.3 Example 18 40.1 18.3 TaC 100 60 40.1 18.3 Example 19 61.0
18.3 TaC 100 60 61.0 18.3 Example 20 51.0 18.3 TaC 100 60 51.0 18.3
Example 21 51.0 18.3 TaC 100 60 51.0 18.3 Example 22 51.0 18.3 TaC
100 60 51.0 18.3 Example 23 51.0 18.3 TaC 100 60 51.0 18.3 Example
24 51.0 18.3 TaC 100 60 51.0 18.3 Example 25 51.0 18.3 TaC 100 60
51.0 18.3 Example 26 51.0 18.3 TaC 100 60 51.0 18.3 Example 27 51.0
18.3 TaC 100 60 51.0 18.3 Example 28 51.0 18.3 TaC 100 60 51.0 18.3
Example 29 51.0 18.3 TaC 70 60 35.7 12.8 Example 30 35.7 12.8 TaC
100 60 35.7 12.8 Example 31 51.0 18.3 TaC 100 60 51.0 18.3
Comparative 51.0 18.3 TaC 50 60 25.5 9.2 Example 1 Comparative 51.0
18.3 TaC 30 60 15.3 5.5 Example 2 Comparative 62.9 18.3 TaC 100 60
62.9 18.3 Example 3 Comparative 51.0 18.3 60 Example 4 Comparative
51.0 18.3 60 Example 5
TABLE-US-00002 TABLE 2 Components of curable composition Inorganic
particles (A) Other particles (A2) Colorant Content in Content in
Content in curable composition curable composition inorganic (% by
mass) (% by mass) particles (A) In solid In curable In solid In
curable Type (% by mass) contents composition Type contents
composition Example 1 Example 2 Si0.sub.2 30 15.3 5.5 Example 3
Si0.sub.2 45 22.9 8.2 Example 4 Example 5 Example 6 Example 7
Example 8 Example 9 Example 10 Example 11 Example 12 Example 13
Example 14 Example 15 Example 16 Example 17 Example 18 Example 19
Example 20 Example 21 Example 22 Example 23 Example 24 Example 25
Example 26 Example 27 Example 28 Example 29 CB 30 15.3 5.5 Example
30 PY150 15.3 5.5 Example 31 Comparative SiO.sub.2 50 25.5 9.2
Example 1 Comparative SiO.sub.2 70 35.7 12.8 Example 2 Comparative
Example 3 Comparative TiC 100 51.0 18.3 Example 4 Comparative TiN
100 51.0 18.3 Example 5
TABLE-US-00003 TABLE 3 Components of curable composition
Polymerizable compound (B) Polymerization initiator (C) Content In
Content in curable composition curable composition B/A (% by mass)
C/A (% by mass) (based on In solid In curable (based on In solid In
curable Type mass) contents composition Type mass) contents
composition Example 1 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 2
M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 3 M1 0.37 18.9 6.8 I-1
0.11 5.5 1.96 Example 4 M1 0.37 21.1 6.8 I-1 0.11 6.1 1.96 Example
5 M1 0.37 15.1 6.8 I-1 0.11 4.4 1.96 Example 6 M1 0.37 19.0 6.8 I-1
0.11 5.5 1.96 Example 7 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example
8 M1 0.37 20.5 6.8 I-1 0.11 5.9 1.96 Example 9 M1 0.37 15.7 6.8 I-1
0.11 4.5 1.96 Example 10 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example
11 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 12 M1 0.37 18.9 6.8
I-1 0.11 5.5 1.96 Example 13 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96
Example 14 M1 0.37 19.0 6.8 I-1 0.11 5.5 1.96 Example 15 M1 0.37
18.9 6.8 I-1 0.11 5.5 1.96 Example 16 M1 0.37 20.8 6.8 I-1 0.11 6.0
1.96 Example 17 M1 0.37 15.0 6.8 I-1 0.11 4.3 1.96 Example 18 M1
0.91 36.3 16.6 I-1 0.11 4.3 1.96 Example 19 M1 0.05 3.1 0.92 I-1
0.11 6.5 1.96 Example 20 M1 0.37 18.9 6.8 I-2 0.11 5.5 1.96 Example
21 M1 0.37 18.9 6.8 I-3 0.11 5.5 1.96 Example 22 M1 0.37 18.9 6.8
I-1 0.11 5.5 1.96 Example 23 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96
Example 24 M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 25 M2 0.37
18.9 6.8 I-1 0.11 5.5 1.96 Example 26 M3 0.37 18.9 6.8 I-1 0.11 5.5
1.96 Example 27 M4 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 28 M1
0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 29 M1 0.37 18.9 6.8 I-1
0.11 5.5 1.96 Example 30 M1 0.53 18.9 6.8 I-1 0.15 5.5 1.96 Example
31 M1 0.37 19.0 6.8 I-1 0.11 5.5 1.96 Comparative M1 0.37 18.9 6.8
I-1 0.11 5.5 1.96 Example 1 Comparative M1 0.37 18.9 6.8 I-1 0.11
5.5 1.96 Example 2 Comparative 0 0 0 I-1 0.11 6.7 1.96 Example 3
Comparative M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 4
Comparative M1 0.37 18.9 6.8 I-1 0.11 5.5 1.96 Example 5
TABLE-US-00004 TABLE 4 Components of curable composition Resin (E)
Polymerization inhibitor (D) Dispersant (E1) Content in curable
Content in curable Content in curable composition composition
composition D/A (% by mass) (% by mass) (% by mass) (based on In
solid In curable In solid In curable E1/A In solid In curable Type
mass) contents composition contents composition Type (based on
mass) contents composition Example 1 PI-1 0.00014 0.0070 0.0025
24.5 8.8 A 0.3 15.3 5.5 Example 2 PI-1 0.00014 0.0070 0.0025 24.5
8.8 A 0.3 15.3 5.5 Example 3 PI-1 0.00014 0.0070 0.0025 24.5 8.8 A
0.3 15.3 5.5 Example 4 PI-1 0.00014 0.0078 0.0025 15.8 5.1 A 0.1
5.6 1.8 Example 5 PI-1 0.00014 0.0056 0.0025 39.8 17.9 A 0.8 32.5
14.6 Example 6 PI-1 0.0001 0.0050 0.0018 24.5 8.8 A 0.3 15.3 5.5
Example 7 PI-1 0.00049 0.0248 0.0089 24.5 8.8 A 0.3 15.3 5.5
Example 8 PI-1 0.00014 0.0075 0.0025 18.3 6.1 A 0.3 16.6 5.5
Example 9 PI-1 0.00014 0.0058 0.0025 37.3 16.1 A 0.3 12.7 5.5
Example 10 PI-1 0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5
Example 11 PI-1 0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5
Example 12 PI-1 0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5
Example 13 PI-1 0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5
Example 14 N/A 0 0 0 24.5 8.8 A 0.3 15.3 5.5 Example 15 PI-1
0.00077 0.0390 0.014 24.5 8.8 A 0.3 15.3 5.5 Example 16 PI-1
0.00014 0.0076 0.0025 17.3 5.7 A 0.3 16.8 5.5 Example 17 PI-1
0.00014 0.0055 0.0025 40.5 18.4 A 0.3 12.1 5.5 Example 18 PI-1
0.00014 0.0055 0.0025 19.3 8.8 A 0.3 12.0 5.5 Example 19 PI-1
0.00014 0.0083 0.0025 29.3 8.8 A 0.3 18.3 5.5 Example 20 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 21 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 22 PI-1
0.00014 0.0070 0.0025 24.5 8.8 B 0.3 15.3 5.5 Example 23 PI-1
0.00014 0.0070 0.0025 24.5 8.8 C 0.3 15.3 5.5 Example 24 PI-1
0.00014 0.0070 0.0025 24.5 8.8 D 0.3 15.3 5.5 Example 25 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 26 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 27 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 28 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 29 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 30 PI-1
0.0002 0.0070 0.0025 24.5 8.8 A 0.43 153 5.5 Example 31 PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Comparative PI-1
0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 1 Comparative
PI-1 0.00014 0.0070 0.0025 24.5 8.8 A 0.3 15.3 5.5 Example 2
Comparative PI-1 0.00014 0.0086 0.0025 30.3 8.8 A 0.3 18.9 5.5
Example 3 Comparative PI-1 0.00014 0.0070 0.0025 24.5 8.8 A 0.3
15.3 5.5 Example 4 Comparative PI-1 0.00014 0.0070 0.0025 24.5 8.8
A 0.3 15.3 5.5 Example 5
TABLE-US-00005 TABLE 5 Components of curable composition Resin (E)
Alkali-soluble resin (E2) Surfactant (F) Content in curable Content
in curable composition composition (% by mass) (% by mass) E2/A In
solid In curable F/A In solid In curable Type (based on mass)
contents composition Type (based on mass) contents composition
Example 1 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 2 A-1
0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 3 A-1 0.18 9.2 3.3
F-1 0.0012 Balance Balance Example 4 A-1 0.18 10.3 3.3 F-1 0.0012
Balance Balance Example 5 A-1 0.18 7.3 3.3 F-1 0.0012 Balance
Balance Example 6 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance
Example 7 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 8 A-1
0.03 1.7 0.55 F-1 0.0012 Balance Balance Example 9 A-1 0.58 24.5
10.6 F-1 0.0012 Balance Balance Example 10 A-1 0.18 9.2 3.3 F-1
0.0012 Balance Balance Example 11 A-1 0.18 9.2 3.3 F-1 0.0012
Balance Balance Example 12 A-1 0.18 9.2 3.3 F-1 0.0012 Balance
Balance Example 13 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance
Example 14 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 15
A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 16 A-1 0.01 0.5
0.18 F-1 0.0012 Balance Balance Example 17 A-1 0.7 28.4 12.9 F-1
0.0012 Balance Balance Example 18 A-1 0.18 7.2 3.3 F-1 0.0012
Balance Balance Example 19 A-1 0.18 11.0 3.3 F-1 0.0012 Balance
Balance Example 20 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance
Example 21 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 22
A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 23 A-1 0.18 9.2
3.3 F-1 0.0012 Balance Balance Example 24 A-1 0.18 9.2 3.3 F-1
0.0012 Balance Balance Example 25 A-1 0.18 9.2 3.3 F-1 0.0012
Balance Balance Example 26 A-1 0.18 9.2 3.3 F-1 0.0012 Balance
Balance Example 27 A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance
Example 28 A-2 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 29
A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 30 A-1 0.26 9.2
3.3 F-1 0.0017 Balance Balance Example 31 A-1 0.18 9.2 3.3 N/A 0 0
0 Comparative A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 1
Comparative A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 2
Comparative A-1 0.18 11.3 3.3 F-1 0.0012 Balance Balance Example 3
Comparative A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example 4
Comparative A-1 0.18 9.2 3.3 F-1 0.0012 Balance Balance Example
5
TABLE-US-00006 TABLE 6 Total solid Evaluation content Light
blocking Temporal Patterning (% by mass) properties stability
properties Example 1 36 A A AA Example 2 36 A A A Example 3 36 B A
B Example 4 32 A B B Example 5 45 A A AA Example 6 36 A A AA
Example 7 36 A A AA Example 8 33 A A A Example 9 43 A A AA Example
10 36 A B A Example 11 36 A B A Example 12 36 A A A Example 13 36 B
A A Example 14 36 A B A Example 15 36 A A A Example 16 33 A A B
Example 17 45 A A A Example 18 46 A A A Example 19 30 A B B Example
20 36 A A A Example 21 36 A A A Example 22 36 A A AA Example 23 36
A A A Example 24 36 A A A Example 25 36 A A AA Example 26 36 A A A
Example 27 36 A A A Example 28 36 A A AA Example 29 36 A A A
Example 30 30 A A A Example 31 36 A A A Comparative 36 C A C
Example 1 Comparative 36 D A D Example 2 Comparative 29 B C C
Example 3 Comparative 36 C A C Example 4 Comparative 36 A A C
Example 5
[0572] Examples and comparative examples are described in Table 1
to Table 6. For example, the curable composition of Example 2
contains the inorganic particles (A) in an amount of 51.0% by mass
in the total solid content of the curable composition (equivalent
to 18.3% by mass with respect to the total mass of the curable
composition). Regarding the type of the inorganic particles, the
curable composition of Example 2 contains TaC (average primary
particle diameter: 60 nm) as the metal carbide-containing particles
(A1) in an amount of 70% by mass (equivalent to 35.7% by mass with
respect to the total solid content of the curable composition and
equivalent to 12.8% by mass with respect to the total mass of the
curable composition) as a content in the inorganic particles (A).
Furthermore, the curable composition of Example 2 contains
SiO.sub.2 as other particles (A2) in an amount of 30% by mass
(equivalent to 15.3% by mass with respect to the total solid
content of the curable composition and equivalent to 5.5% by mass
with respect to the total mass of the curable composition) as a
content in the inorganic particles (A). The curable composition of
Example 2 contains, as the polymerizable compound (B), "Ml" in an
amount of 18.9% by mass with respect to the total solid content of
the curable composition (equivalent to 6.8% by mass with respect to
the total mass of the curable composition). In the curable
composition of Example 2, B/A is 0.37 based on mass. In addition,
the curable composition of Example 2 contains, as the
polymerization initiator (C), "I-1" in an amount of 5.5% by mass
with respect to the total solid content of the curable composition
(equivalent to 1.96% by mass with respect to the total mass of the
curable composition). In the curable composition of Example 2, C/A
is 0.11 based on mass. The curable composition of Example 2
contains, as a polymerization inhibitor, "PI-1" in an amount of
0.0070% by mass with respect to the total solid content of the
curable composition (equivalent to 0.0025% by mass with respect to
the total mass of the curable composition). In the curable
composition of Example 2, D/A is 0.00014 based on mass.
Furthermore, the curable composition of Example 2 contains the
resin (E) in an amount of 24.5% by mass with respect to the total
solid content of the curable composition (equivalent to 8.8% by
mass with respect to the total mass of the curable composition).
The curable composition of Example 2 contains, as the dispersant
(El), "A" in an amount of 15.3% by mass with respect to the total
solid content of the curable composition (equivalent to 5.5% by
mass with respect to the total mass of the curable composition). In
the curable composition of Example 2, E1/A is 0.3 based on mass.
The curable composition of Example 2 contains, as the
alkali-soluble resin (E2), "A-1" in an amount of 9.2% by mass with
respect to the total solid content of the curable composition
(equivalent to 3.3% by mass with respect to the total mass of the
curable composition. In the curable composition of Example 2, E2/A
is 0.18 based on mass. The curable composition of Example 2
contains "F-1" as the surfactant (F). The solid contents of the
curable composition of Example 2 is 36% by mass, and all of the
light blocking properties, the temporal stability, and the
patterning properties of the curable composition of Example 2 were
evaluated as A.
[0573] Other examples and comparative examples may be interpreted
as above.
[0574] The curable compositions of Examples 1 to 31 had excellent
temporal stability and patterning properties, and the cured films
obtained from the curable compositions had excellent light blocking
properties and the effects of the present invention. In contrast,
the curable compositions of Comparative Examples 1 to 5 did not
have the effects of the present invention.
[0575] The curable composition of Example 1 had further improved
effects of the present invention compared to the curable
compositions of Examples 2 and 3 in a case where the content of the
metal carbide-containing particles containing a carbide of group 5
element in the inorganic particles is large.
[0576] The temporal stability and the patterning properties of the
curable composition of Example 1, in which E1/A was equal to or
higher than 0.2, were better than those of the curable composition
of Example 4.
[0577] The patterning properties of the curable composition of
Example 1, in which the content of the alkali-soluble resin was
equal to or greater than 7.3% by mass with respect to the total
solid content of the curable composition, were better than those of
the curable composition of Example 8.
[0578] The patterning properties and the temporal stability of the
curable composition of Example 1, in which the average particle
diameter of the metal carbide-containing particles was larger than
5 nm and less than 200 nm, were better than those of the curable
compositions of Example 10 and Example 11.
[0579] The patterning properties of the curable composition of
Example 1 containing TaC as a metal carbide were better than those
of the curable composition of Example 12 containing NbC as a metal
carbide.
[0580] The patterning properties of the curable composition of
Example 1 containing TaC as a metal carbide were better than those
of the curable composition of Example 13 containing VC as metal
carbide-containing particles. Furthermore, the light blocking
properties of the cured film obtained from the curable composition
of Example 1 were better than those of the cured film obtained from
the curable composition of Example 13.
[0581] The temporal stability and the patterning properties of the
curable composition of Example 1 containing a polymerization
inhibitor were better than those of the curable composition of
Example 14 not containing a polymerization inhibitor.
[0582] The patterning properties of the curable composition of
Example 1 in which D/A was 0.00010 to 0.00050 were better than
those of the curable composition of Example 15.
[0583] The patterning properties of the curable composition of
Example 1 in which E2/A was 0.03 to 0.6 were better than those of
the curable compositions of Example 16 and Example 17.
[0584] The patterning properties and the temporal stability of the
curable composition of Example 1 in which B/A was 0.1 to 0.8 were
better than those of the curable compositions of Example 18 and
Example 19.
[0585] The patterning properties of the curable composition of
Example 1 containing an oxime compound as a polymerization
initiator were better than those of the curable compositions of
Example 20 and Example 21.
[0586] The patterning properties of the curable composition of
Example 1, in which the dispersant had the structural unit
represented by Formula (A1), were better than those of the curable
compositions of Example 23 and Example 24.
[0587] The patterning properties of the curable composition of
Example 1, which contained a (meth)acrylate polymer having 5 to 15
functional groups as a polymerizable compound, were better than
those of the curable compositions of Example 26 and Example 27.
EXPLANATION OF REFERENCES
[0588] 100: solid-state imaging device
[0589] 101: solid-state imaging element
[0590] 102: imaging portion
[0591] 103: cover glass
[0592] 104: spacer
[0593] 105: laminated substrate
[0594] 106: chip substrate
[0595] 107: circuit substrate
[0596] 108: electrode pad
[0597] 109: external connection terminal
[0598] 110: penetration electrode
[0599] 111: lens layer
[0600] 112: lens material
[0601] 113: support
[0602] 114, 115: light blocking film
[0603] 201: light-receiving element
[0604] 202: color filter
[0605] 203: microlens
[0606] 204: substrate
[0607] 205b: blue pixel
[0608] 205r: red pixel
[0609] 205g: green pixel
[0610] 205bm: black matrix
[0611] 206: p-well layer
[0612] 207: reading gate portion
[0613] 208: vertical electric charge transfer path
[0614] 209: element separation region
[0615] 210: gate insulating film
[0616] 211: vertical electric charge transfer electrode
[0617] 212: light blocking film
[0618] 213, 214: insulating film
[0619] 215: planarization film
[0620] 300: infrared sensor
[0621] 310: solid-state imaging element
[0622] 311: infrared absorption filter
[0623] 312: color filter
[0624] 313: infrared transmission filter
[0625] 314: resin film
[0626] 315: microlens
[0627] 316: planarization film
* * * * *